US20230272147A1

US20230272147A1 - Selective polyurethane prepolymer synthesis

Info

Publication number: US20230272147A1
Application number: US18/005,989
Authority: US
Inventors: Klaus Langerbeins; Michael SENZLOBER
Original assignee: PolyU GmbH
Current assignee: PolyU GmbH
Priority date: 2019-03-26
Filing date: 2021-08-12
Publication date: 2023-08-31
Also published as: EP4196513A1; EP3715398A1; WO2021028511A1; WO2020193435A1; EP4013802A1; EP3715397A1; CA3150038A1; US20220372285A1; JP2022546215A; KR20220099536A; WO2020193430A1; WO2022034192A1; KR20210145173A; CN114729092A; JP2022525266A; CN113631606A; US20220235169A1; EP3947498A1; WO2020193432A1; EP3715396A1

Abstract

The present invention relates to a selective process for the preparation of NCO-functionalized polyols, to their use in the preparation of silylated polyurethanes, to processes for preparing silylated polyurethanes and to silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with amino silane and to their use in CASE applications (coatings, adhesives, sealants and elastomers).

Description

The present invention relates to a method for the preparation of polyurethane prepolymers, in particular NCO-functionalized polyols, their use in the preparation of silylated polyurethanes, methods for the preparation of silylated polyurethanes as well as silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with organosilane as well as their use in CASE applications (coatings, adhesives, sealants and elastomers). The method is preferably selective.
Polymers and oligomers that are produced from isocyanate-group-carrying compounds by reaction with hydroxyl or amine functional compounds have been known for a long time and in a wide chemical variety. Depending on the stoichiometry of the reaction and the type of starting compounds, prepolymers having urethane or urea groups are produced, which carry terminally reactive isocyanate, hydroxyl or amine groups and in synthesis either can be further reacted in a subsequent step or can be used as crosslinkable base materials for adhesives and sealants or also as coating agents.
Particularly widespread and of economic importance are urethane prepolymers carrying isocyanate groups (also referred to as “NCO prepolymers”). Furthermore, urethane prepolymers that contain curable functional groups such as silane groups are also known.
In order to obtain polyurethanes with terminal NCO groups, it is customary to react polyfunctional alcohols (also referred to as “polyols”) with an excess of isocyanate-containing compounds, as a rule polyisocyanates. These NCO-terminated polyurethane prepolymers can then serve as starting materials for the preparation of silylated polymers, wherein the NCO prepolymer is reacted with a corresponding aminosilane.
Silylated polyurethanes, which condense (“crosslink”) on contact with water or atmospheric humidity and at room temperature, have been known for some time. They are also referred to as moisture-crosslinking polymers. Inter alia, depending on the content of saline groups and their structure, long-chain polymers, wide-mesh three-dimensional networks, or highly crosslinked systems can form.
Moisture-crosslinking polymers, in particular silylated polyurethanes, have long been used in a wide variety of applications as adhesives and sealants. The range of traditional silicone adhesives and sealants based on dimethylpolysiloxanes and polyurethane adhesives and sealants with free isocyanate groups has thus expanded to include silane-terminated adhesives and sealants.
The conversion of long-chain polyols to NCO prepolymers and subsequent silylation with alkoxysilanes containing NCO-reactive groups was described for example in EP 1093482 A1. Because of the high viscosity of the silane-modified polymers, however, plasticizers and reactive diluents are required in order to bring the viscosity into a processable range.
When they are used in the area of sealing and adhesive systems, highly-viscous silane-modified polymers (SMPs) ordinarily require amounts of 30-50 wt % or 30-70 wt % of inorganic fillers such as calcium carbonate or silicates, which leads to poor processability.
The addition of the plasticizers and diluents required for good processing causes problems due to possible plasticizer migration. The addition of viscosity-reducing reactive diluents or monomeric alkoxysilanes leads to unfavorable costs and higher methanol emissions of the adhesive systems.
EP 1924623 A1 describes for example urethane prepolymers having alkoxysilyl groups that are allophanate-modified and whose allophanate structure has a moisture-curing silane functional radical. In the prior art, attempts are made with the aid of targeted allophanatization to counteract the high viscosities resulting from strong intermolecular hydrogen bridges and dipolar interaction of the urethane, and if applicable, the urea units with one another. Example 1 states that in the most favorable case, the conversion of a PPG (polypropylene glycol) with a molecular weight of approx. 8,000 g/mol (Acclaim 8200) with a starting viscosity of approx. 3000 mPas and the use of secondary aminosilanes leads to polymers with a viscosity of 20,500 mPas.
EP 2468759 A1 also describes urethane prepolymers having alkoxysilyl groups which are modified with substituted aminosilanes. In examples 8-14, PPGs with a molecular weight of approx. 12,000 g/mol (Acclaim 12200) are converted with IPDI in a molar ratio of 1:2.4 into PU prepolymers with a viscosity of 40,000 mPas. The subsequent reaction with different aminosilanes shows the advantage of secondary aminosilanes as endcappers compared to primary aminosilanes. Nevertheless, the lowest viscosity achieved (example 13) was very high at 81,000 mPas, which also speaks for a high content of oligomeric components.
The methods for the production NCO-terminated polyurethane prepolymers described in the prior art often work with a higher excess of polyisocyanate, with the result that the excess polyisocyanates must either be separated by a complex distillation process and/or have a high content of higher oligomers, which in term negatively affects the viscosity of the product. In long-chain polyols in particular, oligomer formation leads to a significant increase in viscosity and considerable drawbacks in the processability or further use of such NCO prepolymers.
At the same time, the methods described in the prior art for the preparation of silylated polyurethanes often yield extremely high-viscosity products, which make further processing and formulation of the polymers more difficult. In this case, the viscosity of the silylated polymers is already affected to a considerable degree by the viscosity of the previously produced NCO-terminated polyurethane prepolymers.
There is thus a continuing need for polyurethane polymers carrying NCO terminal groups as well as the silylated polyurethanes resulting therefrom that have low viscosities and are therefore suitable for a broad scope of application. In particular, simple processing at room temperature is also desired.
Furthermore, in the preparation of the starting products for the silylated polyurethanes, it is a fact that the polymers carrying NCO groups (also abbreviated as “polyurethane prepolymers”), usually unreacted monomers of the isocyanate used in excess, remain in the prepolymer regardless of the reaction time. This residual content of monomeric isocyanate (“residual monomer content”) can have a disruptive effect on the application of NCO prepolymers or the further processing thereof, e.g. into silylated polyurethanes. The content of monomeric isocyanate in these products can be more than 50 wt %. Monomeric isocyanates such as e.g. the aromatic toluene diisocyanate (TDI), the aliphatic hexamethylene-1,6-diisocyanate (HDI) and the cycloaliphatic isophorone diisocyanate (IPDI), have a vapor pressure that is already noticeable at room temperature and therefore have a toxic effect in spray applications in particular because of the resulting isocyanate vapors. In application or reaction at elevated temperatures, as are often required for example in processing of or into adhesives, however, the isomers of the diphenylmethane diisocyanate (MDI) also form aerosol or gaseous emissions.
As the toxicity of the monomeric isocyanates limits the applicability and usability of these NCO prepolymers or makes costly safety measures to protect those processing them or special protective measures during transport and storage necessary, as a rule, prior additional measures for purifying such NCO-functionalized prepolymers are necessary. In the worst case, such (intermediate) products, e.g. also based on government requirements, cannot be used or implemented.
The object of the present invention was therefore to overcome at least one drawback of the prior art. In particular, the object was to provide silylated polyurethanes with the lowest possible viscosities.
According to the invention, this object is achieved by providing silylated polyurethanes obtainable according to claim 1. These are obtainable by a reaction of NCO-functionalized polyol with organosilane. Particularly preferred is the reaction with at least one aminosilane. Most preferred are silylated polyurethanes from a reaction of NCO-functionalized polyol with at least one aminosilane, wherein the NCO-functionalized polyol used was produced by means of a reaction of at least one asymmetrical isocyanate-containing compound (A) with at least one polyol (B) which has a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol and wherein the molar ratio of NCO groups to OH groups is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1. Advantageous improvements are the subject matter of the subclaims or the independent claims. Compositions containing the NCO-functionalized polyols used according to the invention or the silylated polyurethanes according to the invention are also the subject matter of the invention. Furthermore, the use of NCO-functionalized polyols, in particular in preparing silylated polyurethanes as well as methods for the preparation of silylated polyols, is also subject matter of the invention. Moreover, the use or further processing of such produced silylated polyurethanes, in particular in CASE applications (coatings, adhesives, sealants and elastomers) and/or elastomeric material, is also the subject matter of the invention.
According to the invention, silylated polyurethanes can be processed particularly well. For example, these silylated polyurethanes according to the invention can also subsequently show advantageous material properties in their respective end products.
Both the NCO-functionalized polyols used according to the invention themselves and the silylated polyurethanes produced therefrom advantageously show a low residual monomer content. This results in particular from the prior synthesis of the NCO-functionalized polyols. Accordingly, it is possible to strongly limit processing or cleaning steps (such as e.g. distillation). Ideally, these steps can be dispensed with altogether.
A particular advantage of the invention is thus that ideally, the NCO-functionalized polyols used do not require any further purification step after their production in order to show low residual monomer content of the isocyanate-containing compound(s) used. This residual monomer content, which is as low as possible, can further have a positive effect on the silylated polyurethanes according to the inventions, their compositions and their formulations. Advantageously, the residual monomer content is less than (<) 1 wt %, preferably less than or equal to (≥) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %. Furthermore, the silylated polyurethanes according to the invention can remain “additive-free,” as they can already inherently have suitable and advantageous viscosities according to the invention. The silylated polyurethanes according to the invention are therefore preferably free of plasticizers and/or diluents.
Ordinarily required additives intended to influence the viscosities of silylated polyurethanes or compositions thereof as a rule have a negative effect on subsequent product properties (e.g. Shore hardness, tensile strength, or general product longevity, migration behavior). In particularly advantageous embodiments, the silylated polyurethanes according to the invention can already allow, simply by the production thereof, i.e. due to a reaction of NCO-functionalized polyol with organosilane, preferably with at least one aminosilane, a reduction in viscosity of at least 20%. The lower viscosity in each case refers to a direct comparison with silylated polyurethanes that were produced with conventional NCO-functionalized polyurethane prepolymers, i.e. with oligomeric or polymeric NCO-functionalized polyurethane prepolymers.
In addition, it was surprisingly found that by kinetically controlled guidance of the reaction of isocyanate-containing compounds and hydroxyfunctionalized polymers, NCO-terminated polyurethane prepolymers (here also only “polyurethane prepolymers”) with a narrow molecular weight distribution can be prepared, and in particular that in this manner, NCO-functionalized polyols used according to the invention can be prepared. These show particularly low viscosity. In this case, the reaction kinetics are determined in particular by the parameters of reaction temperature and type and amount of catalyst, as well as reaction time.
The inventors therefore succeeded, for the preparation of the silylated polyurethanes according to the invention, in providing particularly suitable NCO-functionalized polyurethane prepolymers, so-called NCO-functionalized polyols. By means of kinetically controlled synthesis or reaction of polyols with isocyanate-containing compounds, NCO-functionalized polyols result herefrom. This means that as a reaction product of this reaction, NCO-functionalized polyols in particular are obtained, while the formation of oligomeric or even polymeric NCO-functionalized compounds, i.e. those composed of at least two polyol molecules linked to one another via urethane bonds, is sharply reduced. The method is therefore selective for NCO-functionalized polyols.
“Selective” means in the context of the invention that the main product obtained from the reaction of isocyanate-containing compounds with polyols is the desired product, in the present case a polyurethane prepolymer having a narrow molecular weight distribution. In particular, it is an NCO-functionalized polyol.
According to the invention, “main product” is always the product that has a content or fraction on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %. The person skilled in the art knows that a chemical reaction always results in a composition of the desired product, the auxiliaries and possible byproduct(s) used, as well as residual contents of the reactants used. Persons skilled in the art are therefore always interested in optimizing reactions in the direction of a more selective, and in the most optimal case, complete reaction of the reactants to yield the desired products.
According to the invention, the term “NCO-functionalized polyol” therefore describes a compound that is composed of one part polyol and n parts isocyanate-containing compound, wherein n is at least 2. The designated component “polyol” denotes the origin of the backbone (hence of the reactant used, the polyol). The previous OH functionalities of the polyol used react here in each case with an isocyanate-containing compound, so that a “polyol with NCO functions,” i.e. an NCO-functionalized polyol, is obtained. Here, “NCO” refers to the isocyanate groups resulting from the isocyanate-containing compound(s) used. These, instead of the previous free hydroxide groups (also OH groups or hydroxy groups), are now available for further reactions (e.g. for a reaction with organosilane to yield silylated polyurethanes).
The NCO-functionalized polyol can also be represented by general structure (1),

- wherein

R^isodenotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R^polydenotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B). The number of free OH groups in the polyol, i.e. per molecule, also refers to the “functionality” of the polyol.
The structure of the NCO-functionalized polyols used according to the invention can also be described by an A_nB-structure, wherein A denotes the isocyanate-containing compound(s) used for preparing the NCO-functionalized polyol, preferably an isocyanate-containing compound, B denotes the polyol used and n corresponds to the number of free OH groups in the polyol used (B).
The term “polyol” is generally understood by the person skilled in the art to be the collective term for polyhydric alcohols, i.e. organic compounds that contain at least two hydroxide groups in the molecule (also referred to as hydroxyfunctionalized polymers). Particularly preferred are for example polyether polyols or polyester polyols. In the case of polyether polyols, alkylene glycols in each case form the backbone of the polyol as repeating units. Polyester polyols are composed of the repeating units of carboxylic acid esters or carbonates or from copolymers thereof.
The collective term “isocyanates” comprises all isocyanate-containing compounds that carry at least one isocyanate group. The term “polyisocyanates” comprises all isocyanate-containing compounds with at least two isocyanate groups.
By guiding the process control in a manner generally known to the person skilled in the art, selective NCO-terminated polyurethane prepolymers can be prepared. The selectivity of the reaction can be represented by an analysis of the molecular weight distribution. The polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, can thus be characterized by their molecular weight distribution.
In this manner, the selectivity of the reaction for the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, can be checked and represented for example by means of gel permeation chromatography (abbreviated as GPC). On an elugram obtained by examining polyurethane prepolymer or NCO-functionalized polyol by means of GPC, the elution volume, which progresses with the continuous flow of the eluate, can be plotted against the signal intensities associated therewith. The course of the elugram indicates “when,” i.e. at which elution volume (V, mL) which component of the sample is detected by the detector. In this case, the components with high molecular weights are detected first, followed later by those with low molecular weights. The continuous course of measurement give rise to a curve with rising and falling areas (i.e. the intensity of the signal rises or falls). The height of the intensity and the area integral thereunder indicate, inter alia, in which amounts the respective components are present in the sample, independently of the injected sample concentration.
By means of a comparison of the elution volume of a sample component of unknown molecular weight to the elution volume of molecules of known molecular weight (comigration standard), a corresponding molecular weight distribution can be obtained by comparison with the graphs produced or computationally by a standardized regression analysis. From this, a corresponding molecular weight distribution can be obtained as an inverse plot of the molar weights against the corresponding signal intensities of the eluted sample. This plot is referred to herein as the course of molecular weight. In this case, the course begins on the x axis of the diagram with smaller sample components of lesser molecular weights and correspondingly reflects the intensity signals of the higher molecular weights as it progresses along the x axis.
The course of the molecular weight of the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, indicates in a range of 2,000 Da (x₁) to 200,000 Da (x₃) along the x axis that it has a first section with an area integral F_Iand a second section with an area integral F_II, the ratio of which F_II/F_Iis between 0 to 0.4 inclusively, preferably between 0.05 and 0.39, particularly preferably between 0.1 and 0.38, wherein the first section extends from x₁to x₂and the second section extends from x₂to x₃, and x₂defines the extreme point between the (last) intensity maximum in the first section (M1a), which lies in the region of the molecular weight of the hydroxyfunctionalized polymer (see FIG. 1) and the first intensity maximum subsequent thereto in the second section (M2).
In the present case, “extreme point” preferably describes a low point or also an intensity maximum.
“Molecular weight” can be used as a synonym for the term “molar weight” or “molar mass.” It can be indicated both in Daltons (Da) or synonymously in grams per mole (g/mol).
FIG. 1 describes the course of molecular weight for calculating the ratios of the area integrals (F_II/F_I). It shows the course of such a curve of molecular weight in a range of 2,000 to 200,000 Da (a synonym of Da is also g/mol).
One or more further intensity maxima (e.g. M1 b) are optionally present in the first section. The area integrals of all these maxima in the first section form the area integral F_I(F_I=F(M1a)+F(M1b)+ . . . ).
One or more further intensity maxima (e.g. M2a) can also be present in the second section. Each area integral of the intensity maxima (M2) present in the second section goes into the sum of the area integral F_II(F_II=F(M2a)+F(M2b)+ . . . ). According to the invention, the ratio of F_IIto F_Iis in the range between 0 and 0.4 inclusively, preferably between 0.05 and 0.39 inclusively, and particularly preferably between 0.1 and 0.38 inclusively.
The position of the intensity maximum M1a is in the range of the molecular weight of the respective hydroxyfunctionalized polymer (polyol) used. It follows from this that the position of x₂also depends on the molecular weight of the hydroxyfunctionalized polymer used.
Accordingly, the intensity maximum M1a lies in the molecular weight region of the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention of formula (1) below,

- Where, n=x+y
  - n corresponds to number of OH groups in the polyol/functionality
    wherein R^isodenotes the structural unit of the isocyanate-containing compound (A) and R^polydenotes the structural unit of the hydroxyfunctionalized polymer, wherein n is equal to x+y and n corresponds to the number of OH groups in the polyol (functionality).

The area F_Ithus corresponds to the molecular weight region of the polyurethane prepolymer, in particular the NCO-functionalized polyol, which is obtained by reacting an NCO group of the polyisocyanate. F_IIcorresponds to the molecular weight region of the higher oligomers, wherein oligomers, which are reaction products generated in the preparation of the NCO-terminated prepolymers in which the polyisocyanates used have reacted with more than one NCO group, such as e.g. allophanate, biuret reaction products, isocyanurates and oligomer blocks, are longer than isocyanate-polymer-isocyanate.
For the computer-controlled software, System PSS WinGPC UniChrom V 8.31, Build 8417 from PSS GmbH, Germany, is preferably used.
Polyurethane prepolymers are obtainable by a reaction of

- I. at least one isocyanate-containing compound with a molecular weight of 120 g/mol to 1000 g/mol with
- II. a hydroxyfunctionalized polymer with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90000, particularly preferably from 4,000 to 80,000 g/mol,
  in the presence of a catalyst.
  preferred are the NCO-functionalized polyols used (or “applied”) according to the invention obtainable due to a reaction of
- I. at least one isocyanate-containing compound (A) with
- II. at least one polyol (B), in the presence of at least one catalyst,
  wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.

In the reaction of I with II, it is preferable for the isocyanate-containing compound (A) to have a molecular weight of 120 g/mol to 1000 g/mol.
Furthermore, it is preferable for the polyol (B) in the reaction of I with II to have a number average weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol.
The reaction of I with II is suitably carried out at temperatures less than or equal to 80° C., in particular at temperatures of 15 to 70° C., preferably at temperatures of 25 to 65° C.
In a preferred embodiment, the isocyanate-containing compound (A) is a diisocyanate. Particularly preferred is an embodiment in which the isocyanate-containing compound (A) is asymmetrical.
As the person skilled in the art is aware, in this context, “asymmetrical” means that the isocyanate-containing compound (A) has no mirror plane in the molecule itself. Furthermore, the NCO groups contained in the asymmetrical isocyanate-containing compound have different steric environments of the NCO groups, which in turn leads to different reactivities thereof. Particularly suitable asymmetrical isocyanate-containing compounds for this purpose are: isophorone diisocyanate (IPDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI) or 2,4-toluene diisocyanate (2,4-TDI, also abbreviated as TDI) or mixtures thereof. In a particularly preferred embodiment, IPDI is used as the isocyanate-containing compound (A).
Because of the conversion of the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, into silylated polyurethanes, there is no significant change in molecular weight distribution, which also allows calculation of the area quotient according to the invention based on the silylated polyurethanes; with the proviso that no water-induced condensation of the silylated polyurethane takes place.
The NCO-functionalized polyol used according to the invention obtainable from the reaction of I with II has, after the reaction is carried out, a content of NCO-functionalized polyol according to the structure perfection A_nB or the general structure (1) on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %.
In the present invention, the molecular weight of the molecular weight distribution obtained by GPC is measured under the following conditions:
The columns are tempered in an oven heated to 70 degrees Celsius. THE (tetrahydrofuran) is fed as a solvent at a flow rate of 1 ml per min into the columns maintained at this temperature, and 50 to 200 μl of a THE sample solution of a polyurethane prepolymer, in particular the NCO-functionalized polyol, is injected for measurement at a sample concentration 0.5 to 1.5 g/L.
In measurement, the molecular weight distribution assigned to the sample and the count number for the outflow time are calculated from the relationship between the logarithmic value of a calibration curve prepared using multiple types of monodisperse polystyrene standard samples.
Suitable as standard polystyrene samples for preparing the calibration curve are e.g. samples with molecular weights Mp [Da] of: 66,000; 42,400; 25,500; 15,700; 8,680; 6,540; 4,920; 3,470; 2,280; 1,306; 370; 266, which are obtainable from PSS Polymer Standards Service GmbH, Mainz; Germany. A refractive index detector (RI detector) is used as a detector.
The GPC columns can preferably be used in combination with a plurality of commercially available polystyrene gel columns. For example, they can preferably consist of a combination of Agilent columns PLGEL 5 μm MIXED-D, 7.5×300 mm, PLGEL 3 μm MIXED-E, 7.5×300 mm, wherein the combination consists of three columns, wherein the first two columns are the PLGEL 5 μm MIXED-D and the third column is the PLGEL 3 μm MIXED-E, 7.5×300 mm.
In the examples described below, the molecular weight distribution of the polyurethane prepolymer, in particular the NCO-functionalized polyol, is measured under the respective conditions indicated.
In the reaction for the preparation of polyurethane prepolymers, in the reaction of I with II the molar ratio of NCO groups to hydroxyl groups is preferably selected to be from 5.0:1 to 1.05:1, preferably from 4:1 to 1.5:1 and particularly preferably from 3.0:1 to 1.8:1.
In the reaction for preparing the NCO-functionalized polyols used according to the invention, in the reaction of I with II, the molar ratio of NCO groups to hydroxyl groups is preferably selected to be from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.
According to an embodiment, the NCO-functionalized polyols obtained from the reaction of I with II have a residual monomer content, i.e. a residual content of isocyanate-containing compound (A) not reacted with the polyol, of less than (<) 1 wt %, preferably less than or equal to (≥) 0.5 wt %, particularly preferably less than or equal to (≥) 0.1 wt % based on the weight of the NCO-functionalized polyol. Determination of the residual monomer content, i.e. a quantitative determination of the remaining isocyanate-containing compound (A) used after completed synthesis of the NCO prepolymers, in particular the NCO-functionalized polyols, is carried out by means of the HPLC-MS/MS method (CAM-0642303-18E) under the conditions of DIN EN ISO/IEC 17025:2018-03. This method is recognized in the FEICA.
In the context of the invention, “residual content” describes the fraction remaining after a reaction. The residual content or the “residual monomer content” is given in wt %, and is based on the total weight of the reaction product or the reaction products of a reactant used in the reaction, here on the weight of the NCO-functionalized polyol. The respective remaining reactant, of which the residual content is given, has as a rule not been reacted.
Isocyanate-containing compounds (A) have at least one NCO group (=isocyanate group). One can distinguish between the monoisocyanates (z=1) and polyisocyanates (z≥2). The NCO groups can react for example with alcohols to yield urethanes or with amines to yield urea derivatives.
Isocyanate-containing compounds (A) can be described by general formula (VI).
R^x
N═C═O)_z (VI),

- wherein
  - R^xdenotes a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, particularly preferably an optionally substituted, linear, or branched C1 to C20 alkyl group, an optionally substituted, linear, or branched C2 to C20 alkenyl group or an optionally substituted, linear, or branched C2 to C20 alkinyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group, most particularly preferably diphenylmethane, toluene, dicylohexylmethane, hexane or methyl-3,5,5-trimethyl cyclohexyl or
  - R^xdenotes a —(R′)—Si(YR^9/10/11)₃group, wherein R⁹, R¹⁰and R¹¹denote independently of one another H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group,
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - each Y independently denotes either O or a direct bond of the Si atom with the respective radical R⁹, R¹⁰or R¹¹, preferably at least one Y denotes O and
  - z is equal to 1.

For the preparation of the NCO-functionalized polyols used according to the invention, polyisocyanates in particular are used. Polyisocyanates always have at least two isocyanate groups.
As polyisocyanates for the preparation of the polyurethane prepolymer according to the invention, in particular of NCO-functionalized polyol, common commercial isocyanates, in particular polyisocyanates of general formula (VI), can be used
R^x
N═C═O)_z (VI),

- wherein
  - R^xdenotes a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, particularly preferably an optionally substituted, linear, or branched C1 to C20 alkyl group, an optionally substituted, linear, or branched C2 to C20 alkenyl group or an optionally substituted, linear, or branched C2 to C20 alkinyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group, most particularly preferably denotes diphenylmethane, toluene, dicylohexylmethane, hexane or methyl-3,5,5-trimethyl cyclohexyl and
  - z is at least 2.

Examples of suitable polyisocyanates include diphenylmethane diisocyanate (MDI), in particular diphenylmethane-4,4′-diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI), diphenylmethane-2,2′-diisocyanate (2,2′-MDI), 4,4′-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate (=isophorone diisocyanate or IPDI), perhydro-2,4′-diphenylmethane diisocyanate and perhydro-4,4′-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethyl cyclohexane (TMCDI), 1,6-hexamethylene diisocyanate (HDI) or trimer thereof (HDI trimer), 1,4-bis-(isocyanate)cyclohexane, 1,4-bis(isocyanate)benzene (PPDI), 1,3- and/or 1,4-bis-(isocyanatomethyl)-cyclohexane, m- and/or p-xylylene diisocyanate (m- and/or p-XDI), m- and/or p-tetramethyl-1,3-xylylene diisocyanate, bis-(1-isocyanato-1-methylethyl)-naphthalene, 2,4- and 2,6-toluene diisocyanate (TDI), 1,3- and 1,4-phenylene diisocyanate, 2,4-dioxo-1,3-diazetidine-1,3-bis(methyl-m-phenylene)diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3′3′-dimethyl-4,4′4′-diisocyanatodiphenyl (TODI), or mixtures thereof, preferably diphenylmethane-4,4′-diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI) or trimer thereof (HDI trimer) or mixtures thereof, most particularly preferably diphenylmethane-4,4′-diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4′-MD) or isophorone diisocyanate (IPDI), oligomers and polymers of the above-mentioned isocyanates, as well as any desired mixtures of the above-mentioned isocyanates.
Preferred are aromatic, aliphatic or cycloaliphatic polyisocyanates with a molecular weight of 120 g/mol to 1,000 g/mol that possess NCO groups having a different reactivity with respect to diols. The differing reactivity of the NCO groups of the polyisocyanate occurs due to differently adjacent substituents to the NCO groups on the molecule, which, for example by steric shielding, reduced the reactivity of the one NCO group in comparison to the other NCO group and/or due to different bonding of an NCO group to the molecule radical, for example in the form of a primary or secondary NCO group.
Examples of preferred aromatic polyisocyanates are all isomers of toluene diisocyanate (TDI), either in isomer pure form or as a mixture of a plurality of isomeric, naphthalene-1,5-diisocyanate (NDI), naphthalene-1,4-diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4-MDI) as well as mixtures of the 4,4′-diphenylmethane diisocyanate (4,4′-MDI) with the 2,4′-MDI-isomers and 1,3-phenylene diisocyanate.
Examples of preferred cycloaliphatic polyisocyanates are e.g. 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl cyclohexane (isophorone diisocyanate, IPDI), 1-methyl-2,4-diisocyanatocyclohexane or hydration products of the above-mentioned aromatic polyisocyanates, in particular hydrated MDI in isomer pure form, preferably hydrated 2,4′-MDI.
Examples of preferred aliphatic polyisocyanates are 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane and lysine diisocyanate.
Particularly preferred is isophorone diisocyanate, (IPDI) as well as diphenylmethane-2,4′-diisocyanate (2,4′-MDI), as well as diphenylmethane-4,4′-diisocyanate (4,4′-MDI), as well as mixtures thereof. Most particularly preferred is IPDI, as well as mixtures with the aforementioned substances.
Isophorone diisocyanate (IPDI) as well as diphenylmethane-2,4′-diisocyanate (2,4′-MDI) as well as diphenylmethane-4,4′-diisocyanate (4,4′-MDI) as well as mixtures thereof in combinations with further isocyanate-containing compounds can also be used.
Hydroxyfunctional compounds are understood to be hydroxyfunctional polymers. Suitable polyols for the preparation of polyurethane polymers are in particular polyether polyols, polyester polyols and polycarbonate polyols as well as mixtures of these polyols. The hydroxyfunctional compounds preferably have a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000, particularly preferably from 4,000 to 80,000 g/mol.
Preferably, the hydroxyfunctionalized polymer is selected from the group composed of polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene di- and -triols, polyols of higher functionality such as sorbitol, pentaerythritol-initiated polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryl-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO₂polyols, polytetrahydrofuran-based polyether (PTMEG), OH-terminated prepolymers based on the reaction of a polyether- or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols, polyester polyols, or mixtures thereof.
“Polyethers” constitute a class of polymers. They are long-chain compounds comprising at least two identical or different ether groups. According to the invention, one also speaks of polyethers in cases where the polymeric ether groups are interrupted by another group (e.g. by isocyanates that are polymerized in or incorporated or further polymer or oligomer units of other monomeric origin).
Particularly suitable as polyether polyols, also referred to as polyoxyalkylene polyols or oligoetherols, are those that are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule with two or more active hydrogen atom such as e.g. water, ammonia or compounds with a plurality of OH or NH groups such as e.g. 1,2-ethane diol, 1,2- and 1,3-propane diol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butane diols, pentane diols, hexane diols, heptane diols, octane diols, nonane diols, decane diols, undecane diols, 1,3- and 1,4-cyclohexane dimethanol, bisphenol A, hydrated bisphenol A, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, glycerol, aniline, as well as mixtures of said compounds.
In a particular embodiment, polyether polyols with block copolymer structures are used. These can be used by reacting the above-mentioned cyclic ethers with oligomeric starting blocks such as e.g. polyoxytetramethylene, polyoxyethylene, polybutadiene, polyisoprene, polyamide, polycaprolactone, polyurethane with hydroxyalkyl-substituted polydimethylsiloxanes, hydroxyl group-containing polyacrylates or polymethacrylates or polyesters, such as described e.g. in EP 2546278 A1, EP 2271691 A1, EP 2493957 A1 and WO 09/133061 A1.
In another embodiment, copolymers of carbon dioxide and cyclic ethers, in particular propylene oxide, are used. Such copolymers are obtainable by a variety of methods, such as those described in WO 2015/032717 A1, WO 2012/136657 A1, EP 2321364 A1 and WO 2018/158389 A1 using organometallic catalysts such as e.g. DMC and cobalt, and chromium complexes. Because of the high viscosity of these copolymers compared to pure polyethers, the method according to the invention of polyurethane prepolymer synthesis, in particular synthesis of the NCO-functionalized polyols, is particularly advantageous. Such copolymers can also be prepared by reacting alcohols with dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate or phosgene. Particularly suitable are polycarbonate diols, in particular amorphous polycarbonate diols.
Monools can also be used the method according to the invention. In this case, monofunctional alcohols, such as e.g. methanol, undecyl alcohol and isopropanol, are used as starting molecules for the polymerization with cyclic ethers. Oligomeric monofunctional alcohols such as ethoxylated fatty alcohols can also be used.
Polyoxyalkylene polyols, which have a low degree of unsaturation (measured according to ASTM D-2849-69 and given in milliequivalents of unsaturation per gram of polyol (mEq/g)), produced for example with the aid of so-called double-metal cyanide complex catalysts (DMC catalysts), as well as polyoxyalkylene polyols with a higher degree of unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates, can also be used. Particularly suitable are polyoxyethylene polyols and polyoxypropylene polyols, in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols.
Particularly suitable are polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation lower than 0.02 mEq/g as well as polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols and polyoxypropylene triols with a molecular weight of 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol and particularly preferably 4,000 to 80,000 g/mol.
Also particularly suitable are so-called ethylene oxide-terminated (“EO-endcapped”, ethylene oxide endcapped) polyoxypropylene polyols. The latter are special polyoxypropylene polyoxyethylene polyols, which for example are obtained in that pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, are further alkoxylated after completion of the polypropoxylation reaction with ethylene oxide and thus have primary hydroxyl groups. Preferred in this case are polyoxypropylene polyoxyethylene diols and polyoxypropylene polyoxyethylene triols. Furthermore, hydroxyl group-terminated polybutadiene polyols are suitable, such as e.g. those produced by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, as well as their hydration products. Further suitable are styrene-acrylonitrile-grafted polyether polyols, such as those commercially obtainable for example under the brand name Lupranol® from the firm Elastogran GmbH, Germany.
Particularly suitable as polyester polyols are polyesters that carry at least two hydroxyl groups and are produced according to known methods, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and/or aromatic polycarboxylic acids with di- or polyhydric alcohols.
Particularly suitable are polyester polyols produced from di- to trihydric alcohols such as e.g. 1,2-ethane diol, diethylene glycol, 1,2-propane diol, dipropylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, neopentyl glycol, glycerol, 1,1,1-trimethylol propane or mixtures of the above-mentioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as e.g. succinic acid, glutaric acid, adipic acid, trimethyl adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, malic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride or mixtures of the above-mentioned acids, as well as polyester polyols of lactones such as e.g. ε-caprolactone. Particularly suitable are polyester diols, in particular those produced from adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as a dicarboxylic acid or from lactones such as e.g. ε-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butane diol, 1,6-hexane diol, dimer fatt acid diol and 1,4-cyclohexane dimethanol as a dihydric alcohol.
Particularly suitable polyols are polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol.
The viscosity of prepolymers producible according to the method of the invention based on polyols with a molecular weight of M_n12,000 g/mol is preferably in the range of 10,000 to 20,000 mPas. With a molecular weight M_nof 18,000 g/mol, the viscosity is in the range of 40,000 to 50,000 mPas (determined using a Brookfield Rheometer DV-3T Extra at 25° C., spindle size and rotational speed of the spindle were selected such that the torque >90%). It can therefore be at least 30% lower than the viscosity prepolymers not produced according to the method of the inventions.
According to the invention, the method is preferably carried out at temperatures of at least 0° C., preferably at least 20° C. and preferably a maximum of 150° C., in particular a maximum of 80° C. The method according to the invention for the preparation of silylated polyurethanes from a reaction of NCO-functionalized polyol with aminosilane is preferably carried out at temperatures of 15 to 70° C., particularly preferably at temperatures of 25 to 65° C.
Particularly preferably, the temperature in the preparation of the polyurethane prepolymers is between 10° C. and 120° C., preferably between 15° C. to 100° C., particularly preferably between 20° C. and 90° C. and most particularly preferably between 25° C. and 85° C.
Suitable catalysts for the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols, are selected from the group of the metal-siloxane-silanol(ate) compounds as well as organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth, zirconium such as e.g. dibutyltin laurate, zinc octoate or titanium tetraisopropylate or also tertiary amines such as e.g. 1,4-diazabicyclo-[2.2.2]-octane.
The term “catalyst” refers to a substance that decreases the activation energy of a specified reaction and thus increases the reaction speed.
The term “metal-siloxane-silanol(-ate)” refers to all metal siloxane compounds that contain either one or more silanol and/or silanolate groups. In an embodiment of the invention, it is also possible that only metal-siloxane-silanolates are present as catalysts. Provided that no individual distinctions are made among these different arrangements, all combinations are included. In the following, the metal-siloxane-silanol(ate) compounds just described (=metal-siloxane-silanol/silanolate compounds) are also referred to as oligomeric metallosilsesquioxanes, “POMS”, metal silsesquioxanes or metallic silsesquioxanes. These terms are used interchangeably in the following
In an embodiment of the present invention, the metal-siloxane-silanol(ate) compound can be present as a monomer, oligomer and/or polymer for the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, wherein the transition from oligomers to polymers is fluid according to the general definition.
Preferably, the metal or metals in the oligomeric and/or polymeric metal-siloxane-silanol(ate) compound was/were present in a terminal position and/or within the chain.
In the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, the chain-type metal-siloxane-silanol(ate) compound is linear, branched and/or in the form of a cage.
Within the meaning of the invention, a “cage” or an oligomeric or polymeric “cage structure” is understood to mean a three-dimensional arrangement of the chain-type metal-siloxane-silanol(ate) compound, wherein individual atoms of the chain form the corner points of a multi-surface basic structure of the compound. Here, at least two surfaces are spanned by the atoms linked to one another, wherein a common intersection is formed. In an embodiment, the compound is composed for example of a cube-shaped basic structure of the compound. A single-cage structure or also a singularly present cage-structure, i.e. a compound defined by a separately present cage, is represented by structure (IVc).
Compounds having a plurality of cages within the compound can be described by the compounds (II) as well as (Ia) to (Id). According to the invention, a cage can be present in “open” or also “closed” form, depending on whether all corner points are bonded, linked or coordinated in such a manner that a closed cage structure results. An example of a closed cage is represented by structures (III), (IV), (IVb), (IVc).
According to the invention, the term “nuclear” describes the nuclearity of a compound, i.e. how many metal atoms are contained therein. A mononuclear compound has one metal atom, while a multi- or binuclear compound has two metal atoms within one compound. The metals can be directly bonded to one another or linked via their substituents. An example of a mononuclear compound according to the invention is represented e.g. by structures (IV), (IVb), (IVc), (Ia) (Ib) or (Ic); a binuclear compound is represented by structure (Id).
A mononuclear single-cage structure is represented by the metal-siloxane-silanol(ate) compounds (IV), (IVb) and (IVc). Mononuclear double-cage structures are e.g. structures (Ia), (Ib) or (Ic).
The metal-siloxane-silanol(ate) compound, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, preferably comprises an oligomeric metal silsesquioxane.
In particular, the metal-siloxane-silanol(ate) compound, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, comprises a polyhedral metal silsesquioxane.
In an embodiment, the metal-siloxane-silanol(ate) compound has the general formula R*_qSi_rO_sM_t, wherein each R* is independently selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C5 to C10 aryl, —OH and —O—(C1 to C10 alkyl), each M is independently selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of the 1, 2, 3, 4, and 5 main group, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

- q is a whole number from 4 to 19,
- r is a whole number from 4 to 10,
- s is a whole number from 8 to 30, and
- t is a whole number from 1 to 8.

In a further embodiment, the metal-siloxane-silanol(ate) compound has the general formula R^# ₄Si₄O₁₁Y₂Q₂X⁴Z₃, wherein each X is independently selected from the group composed of Si, M¹, -M³L¹ _Δ, M³, or —Si(R⁸)—O-M³L¹ _Δ, wherein M¹and M³independently of each other are selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; each Z is independently selected from the group composed of L², R⁵, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl; each R^#, R⁵, R⁶and R⁷is independently selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; each Y independently denotes —O-M²-L³ _Δ, or two Y are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O— isopropyl, and —O-isobutyl, and each M²is independently selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, each Q independently denotes H, M⁴L⁴ _Δ, —SiR⁸, -M³L¹ _Δ, a single bond linked to M³of X or a single bond linked to the Si atom of the radical —Si(R⁸)—O-M³L¹ _Δ, wherein M³, R⁸and L¹are defined as for X, wherein M⁴is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L⁴is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, with the proviso that at least one X denotes M³, -M³L¹ _Aor —Si(R⁸)—O-M³L¹ _Δ.
The person skilled in the art is aware that the number (Δ) of possible ligands for L¹ _Δ, L² _Δ, L³ _Δ, L⁴ _Δ, is directly derived from the number of free valencies of the metal atom used, wherein the valency number describes the valency of the metal.
In a further embodiment, the metal-siloxane-silanol(ate) compound, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, has the general formula (Y_0.25R^#SiO_1.25)₄(Z_0.75Y_0.25XO)₄(OQ)₂, wherein each X is independently selected from the group composed of Si, M¹, -M³L¹ _Δ, M³, or —Si(R⁸)—O-M³L¹ _Δ, wherein M¹and M³independently of each other are selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O— ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C6- to C10 aryl; each Z is independently selected from the group composed of L², R¹, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl; each R^#, R¹, R⁶and R⁷is independently selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C6- to C10 aryl; each Y independently denotes —O-M²-L³ _Δ, or two Y are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and each M²is independently selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, each Q independently denotes H, M⁴L⁴ _Δ, —SiR⁸, -M³L¹ _Δ, a single bond linked to M³of X or a single bond linked to the Si atom of the radical —Si(R⁸)—O-M³L¹ _Δ, wherein M³, R⁸and L¹are defined as for X, wherein M⁴is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L⁴is selected from the group composed of —OH and —O— (C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, with the proviso that at least one X denotes M³, -M³L¹ _Aor —Si(R⁸)—O-M³L¹ _Δ.
Preferably, the metal-siloxane-silanol(ate) compound has the general formula Si₄O₉R¹R²R³R⁴X¹X²X³X⁴OQ¹OQ²Y¹Y₂Z¹Z²Z³, wherein X¹, X²and X³are selected independently of one another from Si or M¹, wherein M¹is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of L², R¹, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L2 is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl; R¹, R², R³, R⁴, R¹, R⁶and R⁷are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; Y¹and Y²denote independently of each another —O-M²-L³ _Δ, or Y¹and Y²are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and M²is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and X⁴denotes -M³L¹ _Δ or M³and Q¹and Q²in each case denote H or a single bond linked to M³, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O— propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

- or
- X⁴denotes -M³L¹ _Δ and Q²H denotes a single bond linked to M³and Q¹, H, M⁴L⁴ _Δ or —SiR⁸, wherein M⁴is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 2, 3, 4, 5 and 8 and the metals of main groups 1, 2, 3, 4 and 5, in particular from the group composed of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, wherein L⁴is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl,
- or
- X⁴, Q¹and Q²denote independently of one another -M³L¹ _Δ, or
- X⁴denotes —Si(R⁸)—O-M³L¹, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes -M⁴L⁴ _Δ,
- or

X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes a single bond linked to the M³atom of X⁴.
In a further embodiment, the metal silsesquioxane, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, has the general formula (X⁴)(Z¹Y¹X²O)(Z²X¹O₂)(Z³X³O₂)(R¹Y²SiO)(R³SiO)(R⁴SiO₂)(R²SiO₂)(Q¹)(Q²), wherein X¹, X²and X³are selected independently of one another from Si or M¹, wherein M¹is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of L², R⁵, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl; R¹, R², R³, R⁴, R⁵, R⁶and R⁷are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C6- to C10 aryl; Y¹and Y²independently denote —O-M²-L³ _Δ, or Y¹and Y²are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and M²is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and X⁴denotes -M³L¹ _Δor M³and Q¹and Q²in each case denote H or a single bond linked to M³, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O— propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

- or
- X⁴denotes -M³L¹ _Δ and Q²H denotes a single bond linked to M³and Q¹denotes H, M⁴L⁴ _Δ or —SiR⁸, wherein M4 is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 2, 3, 4, 5 and 8 and the metals of main groups 1, 2, 3, 4 and 5, in particular from the group composed of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, wherein L⁴is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C6- to C10 aryl,
- or
- X⁴, Q¹and Q²denote independently of one another -M³L¹ _Δ, or
- X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes -M⁴L⁴ _Δ,
- or
- X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes a single bond linked to the M³atom of X⁴.

In a further sense of the invention, the catalyst based on a metal-siloxane-silanol(ate) compound can be described by structure (II),

- wherein
- X¹, X²and X³are selected independently of one another from Si or M¹, wherein M¹is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of L², R⁵, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl; R¹, R², R³, R⁴, R⁵, R⁶and R⁷are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; Y¹and Y²denote independently of each another —O-M²-L³ _Δ, or Y¹and Y²are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O— butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M²is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn, Bi, and X⁴denotes -M³L¹ _Δor M³and Q¹and Q²in each case denote H or a single bond linked to M³, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn, Bi, or
- X⁴denotes -M³L¹and Q², H denotes a single bond linked to M³and Q¹denotes H, M⁴L⁴ _Δ or —SiR⁸, wherein M⁴is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L⁴is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O— isopropyl, and —O-isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C6- to C10 aryl,
- or
- X⁴, Q¹and Q²denote independently of one another -M³L¹ _Δ,
- or
- X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes -M⁴L⁴ _Δ, or
- X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes a single bond linked to the M³atom of X⁴.

In a further preferred embodiment, the metal-siloxane-silanol(ate) compound, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, has general formula (II), wherein X¹, X²and X³denote independently of one another Si, X⁴denotes -M³L¹ _Δ and Q¹and Q²in each case denote a single bond linked to M³, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O— isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl, R¹, R², R³are selected independently of one another from optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl, Y¹and Y²are taken together and together form —O—.
In an embodiment, the metal-siloxane-silanol(ate) compound according to formula (II), depending on the metal equivalents present, can be present in mononuclear form as a monomer or in multinuclear form as a dimer (binuclear), trimer (trinuclear), multimer (multinuclear) and/or mixtures thereof, so that for example structures according to formulae (Ia) to (Id) are possible.
Further multinuclear metal-siloxane-silanol(ate) compounds that can be used according to the invention are structures (Ia), (Ib), (IC) or (Id),

- wherein
- M is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R (R¹to R⁴) is independently selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C5 to C10 aryl, —OH and —O—(C1 to C10 alkyl). Here, the tetravalent metal M represents a common part of a plurality of cages. The person skilled in the art is aware that the number of bonds to the metal M depends on the valency of the metal. Structural formulae (Ia) to (Ic) are optionally to be adjusted accordingly.

In an embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, a mixture of the metal-siloxane-silanol(ate) compounds according to formulae (II), (Ia), (Ib) and (Ic) is used.
Furthermore, the multinuclear metal-siloxane-silanol(ate) compound according to formula (Id) can have 6-fold coordinated metal centers, so that structures according to formula (Id) are possible

- wherein each M is independently selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R is independently selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C5 to C10 aryl, —OH and —O—(C1 to C10 alkyl).

Within the meaning of the invention, the term “mononuclear” the individually, i.e. singularly present cage structure of the catalyst according to the invention based on a metal-siloxane-silanol(ate) compound. Mononuclear catalysts based on a metal-siloxane-silanol(ate) compound can be encompassed by structure (IV) and also by structures (II) and (III).

- wherein
- X⁴denotes -M³L¹ _Δ, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O— isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; R¹, R², R³and R⁴are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl.

Furthermore, metal silsesquioxanes, which are used for the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, are metal-siloxane-silanol(ate) compounds of general structural formula (III), wherein X⁴denotes -M³L¹ _Δ, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of L², R⁵, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O— propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl and R¹, R², R³, R⁴, R⁵, R⁶and R⁷are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl.
In a particularly advantageous embodiment, polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, can be prepared as a metal-siloxane-silanol(ate) compound by a catalyzed reaction with heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).
Here, the abbreviation “TiPOSS” stands for the mononuclear titanium-metallized silesquioxane of structural formula (IV) and can be used equivalently to “heptaisobutyl POSS-titanium(IV) ethoxide” within the meaning of the invention.
In the reaction for the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, the meta l-siloxane-silanol(ate) compound can preferably represent a mixture containing the structures (II), (Ia), (Ib), (Ic), (Id), (III), (IV), (IVb), (IVc).
In a preferred embodiment, the metal in the meta l-siloxane-silanol(ate) compound is a titanium.
Particularly preferred catalysts from the group of the meta l-siloxane-silanol(ate) compounds are heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and the heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS). Most particularly preferred is the heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).
Organometal compounds suitable as catalysts are tin, bismuth, zinc, zirconium, aluminium- or titanium organic compounds. Also suitable as catalysts are tertiary amines.
Suitable organometal compounds are for example tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂, where R denotes e.g. iso-propyl, n-butyl, iso-butyl), such as isopropyl-n-butyl titanate; titanium-acetylacetonate chelates such as di-isopropoxy-bis(acetylacetonate) titanate, di-isopropoxy-bis(ethyl acetoacetate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethyl acetoacetate) titanate, tri-isopropoxide-bis(acetylacetonate) titanate, zirconium tetraalkylates such as zirconium tetraethylate, zirconium tetrabutylate, zirconium tetrabutyrate, zirconium tetrapropylate, zirconium carboxylates such as zirconium diacetate; zirconium acetylacetonate chelates such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium(bisacetylacetonate), aluminum trisalkylates such as aluminum triisopropylate, aluminum trisbutylate; aluminum acetylacetonate chelates such as aluminum tris(acetylacetonate) and aluminum tris(ethyl acetoacetate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II)-2-ethyl hexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptides, dibutyl mercaptides, dioctyl mercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II)-2-ethyl hexanoate or zinc(II)-neodecanoate, mixtures of bismuth and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids such as bismuth(III)-tris(2-ethylhexanoate) and bismuth(III)-tris(neodecanoate) as well as bismuth complex compounds, organolead compounds such as lead octylate, organovanadium compounds.
Suitable amine compounds are e.g. butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylene diamine, triethylenediamine, guanidine, diphenyl guanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undec-7-ene (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof.
Preferred are tin- or titanium organic compounds.
Preferred organometal compounds as catalysts are dibutyl- and dioctyltin diacetate, -maleate, -bis-(2-ethylhexanoate), -dilaurate, -dichloride, -bisdodecyl mercaptide, tributyltin acetate, bis(β-methoxycarbonyl-ethyl)tin dilaurate and bis(β-acetylethyl)tin dilaurate.
Particularly preferred organometal compounds as catalysts are selected from the group composed of dibutyltin dilaurate (DBTL), tin(II)-2-ethyl hexanoate (tin octoate), zinc(II)-2-ethyl hexanoate, zinc(II)-neodecanoate, bismuth(III)-tris(2-ethylhexanoate), bismuth(III)-tris(neodecanoate) or mixtures thereof.
Most particularly preferred is dibutyltin dilaurate (DBTL).
In a further embodiment, the catalysts are selected from the groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or an amine catalyst.
Preferably, catalyst A and/or B eine tin- or titanium organic compound. The catalyst B is particularly preferably selected from the group of the tin(IV) compounds.
In the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, the total catalyst amount is between 1.0 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the hydroxyfunctionalized polymer used.
In the preparation of polyurethane prepolymers, in using a catalyst from group A, a reaction temperature of between 10° C. and 120° C., preferably between 15° C. to 100° C., particularly preferably between 20° C. and 90° C. and most particularly preferably between 25° C. and 85° C. is used.
It is particularly preferable in preparing the NCO-functionalized polyols used according to the invention that in using a catalyst from group A, a reaction temperature of between 15° C. and 70° C., preferably between 25° C. to 65° C., particularly preferably between 30° C. and 50° C. and most particularly preferably between 35° C. and 45° C. is used.
Furthermore, in the preparation of polyurethane prepolymers, in particular in preparing the NCO-functionalized polyols used according to the invention, it is preferable in using a catalyst from group A that the amount of catalyst A is selected between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm.
In a further preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention as catalyst A, heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) is used.
In a particularly preferred embodiment, in the preparation of polyurethane prepolymers, in using a catalyst from group A, a reaction temperature of 10° C. to 120° C., preferably from 15° C. to 100° C., particularly preferably from 20° C. to 90° C. and most particularly preferably between 25° C. and 85° C. is used, and amount of catalyst A is selected between 1.0 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm.
In another particularly preferred embodiment, in the preparation of polyurethane prepolymers, in use of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as a catalyst from group A, a reaction temperature of 10° C. to 120° C., preferably from 15° C. to 100° C., particularly preferably from 20° C. to 90° C. and particularly preferably from 25° C. to 85° C. is used.
In another particularly preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in use of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as a catalyst from group A, the amount of catalyst A is selected between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm and particularly preferably between 3 ppm and 100 ppm.
In a most particularly preferred embodiment, in the preparation of polyurethane prepolymers, in use of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as a catalyst from group A, a reaction temperature of 10° C. to 120° C., preferably from 15° C. to 100° C., particularly preferably from 20° C. to 90° C. and particularly preferably 25° C. to 85° C. is used, and the amount of catalyst A is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm.
In a further preferred embodiment, in the preparation of polyurethane prepolymers, in using a catalyst from group B, a reaction temperature of 20° C. to 80° C., preferably from 20° C. to 70° C., particularly preferably from 25° C. to 50° C. is used.
It is particularly preferable in preparing the NCO-functionalized polyols used according to the invention that in using a catalyst from group B, a reaction temperature of between 20° C. and 70° C., preferably between 25° C. to 50° C., particularly preferably between 30° C. and 45° C. and most particularly preferably between 35° C. and 45° C. is used.
In a further preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in using a catalyst from group B, the amount of catalyst B is selected between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 100 ppm.
In a particularly preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in using a catalyst from group B, a reaction temperature of 20° C. to 80° C. and preferably from 20° C. to 70° C., particularly preferably from 25° C. to 50° C. is used, and the amount of catalyst B is selected between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 100 ppm.
In a further preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention as catalysts, dibutyltin dilaurate (DBTL) is used.
In another particularly preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in use of dibutyltin dilaurate (DBTL) as catalyst B, a reaction temperature of 20° C. to 70° C., preferably from 25° C. to 50° C. is used.
In another particularly preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in use of dibutyltin dilaurate (DBTL) as catalyst B, the amount of catalyst B is selected between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm, particularly preferably between 40 ppm and 50 ppm.
In a most particularly preferred embodiment, in the preparation of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, in use of dibutyltin dilaurate (DBTL) as catalyst B, a reaction temperature of 20° C. to 70° C., preferably from 25° C. to 50° C., is used and the amount of catalyst B is selected between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm, particularly preferably between 40 ppm and 50 ppm.
In addition, the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, serve as building blocks for the preparation of polyurethane elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems, polyurethane dispersions, which are widely used as polyurethane foams, construction materials, paints, coatings, adhesives and sealants, casting compounds, films, PUR elastomers etc. The polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, also serve as building blocks for the targeted preparation of block copolymers, star polymers or dendrimers.
The isocyanate functional polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, can be directly used as crosslinking components, without further reaction or processing, in reactive PU compositions for example in aqueous 1K- or 2K-PU compositions.
Aqueous 1K PU dispersions are OH or NH functional dispersions in combination with raw materials containing thermically reversible blocked isocyanate groups. Suitable polyisocyanates in this context can for example be used in unmodified form, i.e. in their hydrophobic form, wherein the resin dispersion (OH- or NH-terminated) must have a co-dispersing function. In contrast, hydrophilically modified blocked polyisocyanates themselves form stabile dispersions, and they are mixed with the resin dispersion. However, the blocked isocyanate function can also be directly bonded to the OH- or NH-terminated polymer backbone. Such systems are known as self-crosslinking dispersions.
Aqueous 2K PU dispersions are composed of a binder component and a crosslinker component, which are produced and stored separately from each other and are not mixed together until shortly before application. The processing time or pot life (i.e. the time in which the coating composition according to the invention can be processed, preferably at room temperature (15 to 25° C., in particular 20° C.), without causing, for example due to corresponding crosslinking reactions at room temperature, such a sharp increase in viscosity that application is no longer possible), is known to be dependent on the components used.
According to the most preferred embodiment of the present invention, polyurethane prepolymers, i.e. the NCO-functionalized polyols used according to the invention, are further reacted in a further step with a silane, in particular with an organosilane, preferably with an aminosilane, to yield silylated polyurethanes.
Subject matter of the present invention are therefore silylated polyurethanes obtainable by reaction of polyurethane prepolymers, i.e. the NCO-functionalized polyols used according to the invention with organosilanes, preferably with aminosilanes. According to the invention, one or more organosilanes, preferably one or more aminosilanes, are used. Particularly preferably, an aminosilane, i.e. only one “kind” of aminosilane is used according to the invention.
The silylated polyurethanes obtained in this manner, as well as compositions containing said silylated polyurethanes, are also subject matter of the present invention.
The silylated polyurethanes according to the invention produced from at least one polyurethane prepolymer, i.e. from at least one NCO-functionalized polyol used according to the invention, also have area ratios from the molecular weight distribution (measured by GPC).
The term “silane” or “organosilane” refers to compounds, which on the one hand have at least one, ordinarily two or three hydrolysable groups directly bonded to the silicon atom via Si—O bonds, preferably alkoxy groups or acyloxy groups, and on the other hand have at least one organic radical directly bonded to the silicon atom via a Si—C bond. Silanes that have alkoxy groups or acyloxy groups are also known to the person skilled in the art as organoalkoxysilanes or organoacyloxysilanes.
Accordingly, the term “silane group” refers to the silicon-containing group bonded to the organic radical of the silane via the Si—C. The silanes or their silane groups have the property of undergoing hydrolysis on contact with moisture. In this case, organosilanols, i.e. silicon organic compounds containing one or more silanol groups (Si—OH groups) are formed, and by means of subsequent condensation reactions, organosiloxanes, i.e. silicon organic compounds containing one or more siloxane groups (Si—O—Si groups).
Suitable silanes within the meaning of the invention contain at least one group that is reactive with respect to isocyanate groups.
This reaction is preferably carried out in a stoichiometric ratio of the groups reactive to isocyanate groups to the isocyanate groups of 1:1 or with a slight excess of the groups reactive to isocyanate groups, so that the resulting silane functional polyurethane polymer is free of isocyanate groups.
In the reaction of the silane having at least one group reactive to isocyanate groups with a polyurethane polymer having isocyanate groups, the silane can in principle, although this is not preferred, be used in a substoichiometric amount, so that a silane functional polymer is obtained that has both silane groups and isocyanate groups. The remaining NCO groups can be quenched with compounds that contain a nucleophilic group (OH, SH, NH₂, NHR), e.g. 2-ethylhexyl alcohol, dibutylamine, benzyl alcohol, stearyl amine.
A silane having at least one group reactive to isocyanate groups is for example a mercaptosilane or an aminosilane.
Within the meaning of the invention, “silylated polyurethanes” refers to silane-modified, silane functional or silane-terminated polyurethanes, which are also interchangeably referred to as SPUR. The definition includes polymerizates, polycondensates or polyadducts.
Furthermore, these are moisture-crosslinking, which can cure under the effect of water, either by addition or mixture components of or with water or by being brought into contact with atmospheric humidity, preferably under the additional use of a catalyst.
“Polymers” are chemical compounds of chain or branched molecules (macromolecules), which in turn are composed of a number of identical/similar or also unequal units, the so-called monomers. Polymers also comprise oligomers. Oligomers are polymers that have a smaller number of units. Unless expressly defined otherwise, according to the invention, oligomers fall under the heading of polymers. Polymers can occur as homopolymers (=composed of only one monomer unit), copolymers (=composed of two or more monomer units) or as a polymer mixture (=polymer alloy, polymer blends, i.e. mixtures of different polymers and copolymers).
In general customary use, and also according to the invention, silane functional polymers are also referred to as hybrid polymers. These polymers can combine the curing chemistry of alkoxysilane groups with the chemistry of the polyols or polyurethanes. Alkoxysilane groups are known from silicone chemistry that at least partially contribute isocyanate functional polymers, in particular hydroxyfunctional polymers, to the backbone (“polymer backbone”) of the hybrid polymer. Via the reactive silane end groups, due for example to the entry of atmospheric moisture, crosslinking (“curing”) takes place. The curing mechanism of these systems is preferably neutral.
“Alkoxy” refers to an alkyl group that is bonded via an oxygen atom to the main carbon chain or the main skeleton of the compound.
Silane functional polyurethanes contain a polymer backbone (P) as well as at least two terminal groups or functional groups or modifications of the following general formula (V)

- wherein
  - X is C, Si or a heteroatom, optionally having, depending on its covalency, one or more radicals R⁸, preferably C, N, O, P, S, particularly preferably C, N or O, most particularly preferably N or O and which in each case is bonded to a carbon in the polymer backbone,
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - each Y independently denotes either O or a direct bond of the Si atom to the respective radical R⁹, R¹⁰or R¹¹, and preferably at least one Y denotes O,
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted, linear, or branched C2 to C18 alkinyl group, an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of general structure (Vb),
  - R¹²and R¹⁴in each case denote independently of each other H or a radical from the group composed of —R¹⁵, —COOR¹⁵and —CN,
  - R¹³denotes H or a radical from the group composed of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵and —SO₂OR¹⁵,
  - R¹⁵denotes a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom,
  - R⁹, R¹⁰and R¹¹denote independently of one another H, an optionally substituted, linear, or branched C1 to C20 alkyl group, an optionally substituted, linear, or branched C2 to C20 alkenyl group or an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group, preferably at least R⁹is a C2 alkyl group, particularly preferably at least R⁹and R¹⁰is a C2 alkyl group and
  - m is 0 or 1, and when m=0, the Si atom is directly bonded to a carbon in the polymer backbone (P).

In an alternative embodiment, polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention with an organosilane of formula (IX)

- wherein the two radicals R¹⁶and R¹⁷in each case are independent of each other and the radical R¹⁶is a linear or branched, monovalent hydrocarbon radical with 1 to 8 C atoms, in particular a methyl or ethyl group, the radical R¹⁷is an acyl radical or is a linear or branched, monovalent hydrocarbon radical with 1 to 5 C atoms, in particular a methyl or ethyl group, preferably a methyl group, the index a is 0 or 1 or 2, in particular 0, and the radical R¹⁶is a linear or branched, divalent hydrocarbon radical with 1 to 12 C atoms, which optionally has cyclic fractions and optionally one or more heteroatoms, in particular one or more nitrogen atoms, in particular an alkylene group with 1 to 6 C atoms, preferably 2 to 6 C atoms, in particular a propylene group, can be reacted.

Within a silane group of formula (IX), R¹⁶and R¹⁷in each case denote independently of one another the radicals described. For example, compounds with terminal groups of formula (IX), which are ethoxydimethoxysilane terminal groups (R¹⁶=methyl, R¹⁷=methyl, R¹⁷=ethyl), are therefore also possible.
R¹⁹is a hydrogen atom or a cyclic, linear or branched, monovalent hydrocarbon radical with 1 to 20 C atoms, which optionally has cyclic fractions, or a radical of the following formula:

- wherein the radicals R²⁰and R²¹in each case denote independently of each other a hydrogen atom or a radical from the group composed of —R²³, —COOR²³and —CN, the radical R²²is a hydrogen atom or a radical from the group composed of —CH₂—COOR*, —COOR²³, —CONHR²³, —CON(R²³)₂, —CN, —NO₂, —PO(OR²³)₂, —SO₂R²³and —SO₂OR²³, and the radical R²³is a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom.

R¹⁹can also be a hydrogen radical containing alkoxysilyl groups such as e.g. a trimethoxysilylpropyl radical.
Examples of suitable aminosilanes according to the invention are primary aminosilanes, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane; secondary aminosilanes, preferably N-butyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; products from the Michael like addition of primary aminosilanes, such as products from 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably N-(3-trimethoxysilyl-propyl)-aminosuccinic acid dimethyl- and -diethylesters.
Michael acceptors are compounds that contain double bonds activated by electron acceptor radicals and can therefore undergo nucleophilic addition reactions with primary amino groups (NH₂groups) in a manner analogous to Michael addition (hetero-Michael addition).
Particularly suitable as aminosilanes are secondary aminosilanes, in particular aminosilanes, in which R¹⁹in formula (IX) is different from H. Preferred are N-alkylamino silanes such as N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyl diethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane and N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane.
Suitable mercaptosilanes have general formula (X):
HS—R¹⁸—(SiR¹⁶ _a(OR¹⁷)_3-a) (X)
wherein the radicals R¹⁶to R¹⁸are as defined above. 3-mercaptopropyl trimethoxysilane and 1-mercaptomethyl methyldiethoxysilane can be mentioned as examples.
Mixtures of the above-mentioned silanes according to formula (VIII) and formula (IX) as well as the mercaptosilane (X) can also be used for the endcapping reaction.
In a further embodiment, suitable organosilanes are those comprising all reaction products of the Michael-like addition of primary aminosilanes such as 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxy methylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters and mixtures thereof.
Unless otherwise indicated, N in particular refers to nitrogen. Furthermore, O in particular refers to oxygen, unless otherwise indicated. S in particular refers to sulfur, unless otherwise indicated. P in particular refers to phosphorus, unless otherwise indicated. C in particular refers to carbon, unless otherwise indicated. H in particular refers to hydrogen, unless otherwise indicated. Si in particular refers to silicon, unless otherwise indicated.
“Optionally substituted” means that in the corresponding group or the corresponding radical, hydrogen atoms can be replaced by substituents. Substituents can in particular be selected from the group composed of C1 to C4 alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogeno, fluoro, chloro, bromo, iodo, hydroxy, amino, alkyl amino, dialkyl amino, C1 to C4 alkoxy, phenoxy, benzyloxy, cyano, nitro, and thio. When a group is refer tod as optionally substituted, 0 to 50, in particular 0 to 20, hydrogen atoms of the group can be replaced by substituents. When a group is substituted, least one hydrogen atom is replaced by a substituent.
The term “alkyl group” means a saturated hydrocarbon chain. Alkyl groups in particular have general formula —C_nH_2n+1. The term “C1 to C16 alkyl group” in particular refers to a saturated hydrocarbon chain with 1 to 16 carbon atoms in the chain. Examples of C1 to C16 alkyl groups are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and ethylhexyl. Accordingly, a “C1 to C8 alkyl group” refers in particular to a saturated hydrocarbon chain with 1 to 8 carbon atoms in the chain. Alkyl groups in particular can also be substituted, even when this is not specifically indicated.
“Linear alkyl groups” refers to alkyl groups that contain no branches. Examples of linear alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
“Branched alkyl groups” refers to alkyl groups that are not linear, i.e. in which the hydrocarbon chain also has a branch. Examples of branched alkyl groups are isopropyl, iso-butyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.
“Alkenyl groups” refers to hydrocarbon chains containing at least one double bond along the chain. In particular, for example, an alkenyl group with a double bond has general formula —C_nH₂n⁻¹. However, alkenyl groups can also have more than one double bond. The term “C2 to C16 alkenyl group” in particular refers to a hydrocarbon chain with 2 to 16 carbon atoms in the chain. Here, the number of the hydrogen atoms varies depending on the number of double bonds in the alkenyl group. Examples of alkenyl groups are vinyl, allyl, 2-butenyl and 2-hexenyl.
“Linear alkenyl groups” refers to alkenyl groups having no branches. Examples of linear alkenyl groups are vinyl, allyl, n-2-Butenyl and n-2-hexenyl.
“Branched alkenyl groups” refers to alkenyl groups that are not linear, i.e. in which the hydrocarbon chain in particular also has a branch. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl and 2-ethyl-2-pentenyl.
“Aryl groups” refers to monocyclic (e.g. phenyl), bicyclic (e.g. Indenyl, naphthalenyl, tetrahydronaphthyl, or tetrahydroindenyl) and tricyclic (e.g. fluorenyl, tetrahydrofluorenyl, anthracenyl, or tetrahydroanthracenyl) ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic. In particular, a C4 to C14 aryl group denotes an aryl group having 4 to 14 carbon atoms. Aryl groups can in particular also be substituted, even if this is not specifically indicated.
Within the meaning of the invention, “silanols” are organic silicon compounds in which at least one hydroxyl group (OH) is bonded to the silicon atom (—Si—OH).
Within the meaning of the invention, “silanolates” are organic silicon compounds in which at least one deprotonated hydroxy function (R—O—) is bonded to the silicon atom (—Si—O—), wherein this negatively-charged oxygen atom can also be chemically covalently boded and/or coordinated to further compounds, such as e.g. metals.
According to the invention, the silylated polyurethanes are produced by means of catalyzed synthesis of at least one isocyanate reactive compound, in particular a hydroxyfunctionalized polymer, a polyol (B), and a compound (A) having at least one isocyanate group.
According to the invention, this synthesis takes placed by means of catalyzed synthesis of an isocyanate-reactive compound, in particular a hydroxyfunctionalized polymer, a polyol (B), and a polyisocyanate compound. A polyisocyanate is preferably used.
After this, the prepolymer containing isocyanate groups obtainable in this manner, in particular the NCO-functionalized polyol used according to the invention, are converted with an organosilane into the silylated polyurethane according to the invention.
The subsequent reaction of the polyurethane prepolymer, in particular of the NCO-functionalized polyol with an organosilane of formula (VIII) yields the silylated polyurethane according to the invention

- wherein
  - R⁷is H,
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of general structure (Vb),
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - R¹²and R¹⁴in each case denote independently of each other H or a radical from the group composed of —R¹⁵, —COOR¹⁵and —CN,
  - R¹³denotes H or a radical from the group composed of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵and —SO₂OR¹⁵,
  - R¹⁵denotes a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom,
  - R⁹, R¹⁰and R¹¹denote independently of one another H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, preferably at least R⁹is a C2 alkyl group, particularly preferably R⁹and R¹⁰is a C2 alkyl group and
  - each Y independently denotes either O or a direct bond of the Si atom to the respective radical R⁹, R¹⁰or R¹¹, preferably at least one Y denotes O.

According to the invention, the terminal groups in the silylated polyurethane can be described by general formula (V)

- wherein
  - X is C, Si or a heteroatom, optionally having, depending on its covalency, one or more radicals R⁸, preferably C, N, O, P, S, particularly preferably C, N or O, most particularly preferably N or O, and a carbon is bonded to the polymer backbone,
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, preferably an optionally substituted, linear, or branched C1 to C15 alkyl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - each Y independently denotes either O or a direct bond of the Si atom to the respective radical R⁹, R¹⁰or R¹¹, preferably at least one Y denotes O,
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted, linear, or branched C2 to C18 alkinyl group, an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of general structure (Vb),
  - R¹²and R¹⁴in each case denote independently of each other H or a radical from the group composed of —R¹⁵, —COOR¹⁵and —CN,
  - R¹³denotes H or a radical from the group composed of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵and —SO₂OR¹⁵,
  - R¹⁵denotes a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom,
  - R⁹, R¹⁰and R¹¹denote independently of one another H or a C1 or C2 alkyl group, preferably at least R⁹is a C2 alkyl group, particularly preferably R⁹and R¹⁰is a C2 alkyl group and
  - m is 0 or 1, and when m=0, the Si atom is directly bonded to a carbon in the polymer backbone (P).

In a further alternative embodiment of all of the above combinations, the silylated polyurethane according to the invention is produced by reaction with an organosilane selected from the group of N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-(3-triethoxysilyl-propyl)aminosuccinic acid diethylester or a mixture thereof.
In an alternative embodiment, the polyurethane prepolymer according to the invention, in particular the NCO-functionalized polyol, is produced by catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI).
In an alternative embodiment, the polyurethane prepolymer according to the invention, in particular the NCO-functionalized polyol, is produced by catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) using DBTL.
In an alternative embodiment, the polyurethane prepolymer according to the invention, in particular the NCO-functionalized polyol, is produced by catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI).
In a further alternative embodiment, the silylated polyurethane polymer according to the invention is produced by catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) and subsequent silanization with N-[3-(trimethoxysilyl)propyl]butylamine].
In a further alternative embodiment, the silylated polyurethane polymer according to the invention is produced by catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) and subsequent silanization with N-[3-(trimethoxysilyl)propyl]butylamine] using TiPOSS.
Alternatively, a polypropylene glycol with a number average molecular weight of 18,000 g/mol is used in the above-mentioned embodiments.
In a further alternative embodiment, this additive from the group comprising one or more fillers selected from the group of inorganic and organic fillers, in particular natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearic acid, barite (heavy spar), talcs, quartz flour, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminum silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxides, silicic acids including highly disperse silicic acids from pyrolysis processes, industrially produced carbon blacks, graphite, metal powders such as aluminum, copper, iron, silver, steel, PVC powders or hollow spheres, one or more adhesion promoters from the group of the silanes, in particular aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylene diamine as well as analogs thereof with ethoxy- or isopropoxy groups instead of methoxy groups on the silicon, aminosilanes with secondary amino groups, such as in particular N-phenyl-, N-cyclohexyl- and N-alkylamino-silanes, furthermore mercaptosilanes, epoxysilanes, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes and iminosilanes, as well as oligomeric forms of the silanes, as well as adducts of primary aminosilanes with epoxysilanes or (meth)acrylosilanes or anhydridosilanes. Particularly suitable are 3-glycidoxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-N′-[3-(tri-methoxysilyl)propyl]ethylenediamine, 3-mercaptopropyl trimethoxysilane, 3-ureidopropyltrimethoxysilane and the corresponding silanes with ethoxy groups instead of methoxy groups, as well as oligomeric forms of these silanes, one or more moisture scavengers from the group of silanes, in particular tetraethoxysilane, vinyltrimethoxy- or vinyltriethoxysilane or organoalkoxysilanes which have a functional group at the a position of the silane group, in particular N-(methyldimethoxysilylmethyl)-O-methyl-carbamate, (methacryloxymethyl)silane, methoxymethylsilane, orthoformic acid esters, as well as calcium oxide or molecular sieves, one or more plasticizers from the group of carboxylic acid esters such as phthalates, in particular 1,2-cyclohexane dicarboxylic acid diisononylester, dioctylphthalate, diisononylphthalate or diisodecylphthalate, adipates, in particular dioctyladipate, azelates, sebacates, polyols, in particular polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, citrates, in particular triethyl citrate, organic phosphoric and sulfonic acid esters, polybutenes fatty acid methyl or ethyl esters derived from natural fatts or oils, one or more UV stabilizers from the group of organic (benzophenone, benzotriazole, oxalanilide, phenyltriazine) and inorganic (titanium dioxide, iron oxide, zinc oxide) UV absorbers as well as antioxidants from the group of the sterically hindered phenols, amines, phosphites and phosphonites, one or more thixotropic agents from the group of phyllosilicates such as bentonites, derivatives of castor oil, hydrated castor oil, polyamides, polyurethanes, urea compounds, pyrogenic silicic acids, cellulose ethers or hydrophobically modified polyoxyethylenes, one or more wetting agents from the group of nonionic, anionic and cationic surfactants or combinations thereof.
In a further alternative embodiment, the composition according to the invention additionally contains a water scavenger, preferably a vinylalkoxysilane, particularly preferably vinyltrimethoxysilane (VTMO). In this case, it is always possible that the alkoxy substituents (e.g. -methoxy or -ethoxy) of the alkoxysilanes in the composition of at least one silylated polyurethane with at least one water scavenger can undergo an exchange with one another.
In the preparation of the polyurethane prepolymers according to the invention, in particular the NCO-functionalized polyols and the silylated polyurethanes obtainable therefrom, first either the entire isocyanate-containing compound (component I or also (A)) or however the entire isocyanate-reactive compound, in particular the hydroxyfunctionalized polymer (component II or also (B)) is introduced, after which the respective other component 1/(A) or II/(B) is added, then mixed with at least one catalyst, and the components are reacted. The catalyst can be introduced before component I/(A) and II/(B) or added to the respective component or to a mixture of component I/(A) and II/(B). From the resulting polyurethane prepolymers, in particular the resulting NCO-functionalized polyols used according to the invention, silylated polyurethane according to the invention is then produced by a reaction with the organosilane, in particular with aminosilane. If one or more further components are additionally used, they can in principle be added at any desired point in time to the reaction mixture.
The method according to the invention is preferably carried out under exclusion of (air) moisture and at the pressure of the ambient atmosphere, i.e. about 900 to 1100 hPa.
The method according to the invention can be carried out continuously, e.g. in a tube reactor or tubular reactor with a plurality of metering points positioned next to or also behind one another, or discontinuously, e.g. in a conventional reaction vessel with a stirrer.
In a particularly preferred embodiment, the silylated polyurethanes according to the invention are obtained from a reaction of NCO-functionalized polyol with aminosilane, wherein

- NCO-functionalized polyol has an A_nB-structure, wherein A denotes the isocyanate-containing compound(s) used for preparing the NCO-functionalized polyol and B denotes the polyol used and n corresponds to the number of free OH groups in the polyol used (B) or the NCO-functionalized polyol of general structure (I),

- wherein R^isodenotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R^polydenotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B) (=functionality), and
- the NCO-functionalized polyol was produced due to a reaction of
  - I. at least one asymmetrical isocyanate-containing compound (A) with a molecular weight of 120 g/mol to 1000 g/mol with
  - II. at least one polyol (B) with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol, in the presence of a catalyst and at temperatures of 15 to 70° C., preferably 25 to 65° C., and wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1, and
- the NCO-functionalized polyol obtained therefrom has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A) not reacted with the polyol (B), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol.

It is most preferable in the reaction of I with 11 for the asymmetrical isocyanate-containing compound (A) used in I to be isophorone diisocyanate (IPDI).
Furthermore, it is most preferable in the reaction of I with II for the polyol (B) used in II to be a polyether-polyol or a polyester-polyol, preferably a polyether-polyol. Even more preferable are polyether polyols with a number average molecular weight M_nof 4,000 to 80,000 g/mol.
In a further highly preferred embodiment, the catalyst in the reaction of I with II is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate (DBTL) or a mixture thereof.
In a highly preferred embodiment of the invention, the silylated polyurethane according to the invention is composed of the above-described NCO-functionalized polyols, in that these are reacted with an organosilane, preferably with an aminosilane. Particularly preferable here are aminosilanes selected from the group composed of the primary aminosilanes, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane, the secondary aminosilanes, preferably N-butyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, from the group of the products obtainable from the Michael like addition of primary aminosilanes such as 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid- and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably N-(3-trimethoxysilyl-propyl)-amino-succinic acid dimethyl- and -diethylesters and/or from the group of the N-alkylamino silanes, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane, or mixtures thereof. Most preferable is the aminosilane N-butyl-3-aminopropyl trimethoxysilane.
Moreover, it is preferable to use the silylated polyurethanes in CASE applications (coatings, adhesives, sealants and elastomers) and/or for elastomeric materials.
The soft foams obtained from use of the silylated polyurethanes according to the invention are characterized by a Shore A hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range of 5 to 95, more preferably in the range of 10 to 90, particularly preferably in the range of 15 to 85.
The silylated polyurethanes according to the invention are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have a Shore A hardness in a cured state according to ASTM D2240-15 in the range of 0 to 100, preferably in the range of to 100, more preferably in the range of 20 to 95, particularly preferably in the range of 25 to 90.
Silylated polyurethanes according to the invention are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have an elongation at break in a cured state according to DIN 53504-S2 (:2017-03) in the range of 0 to 1000%, preferably in the range of to 500%, particularly preferably in the range of 50 to 250%.
Accordingly, because of the above-mentioned properties and advantages, it is most particularly preferred to use NCO-functionalized polyols according to one of the above-described embodiments in preparing silylated polyurethanes.
By using NCO-functionalized polyols, silylated polyurethanes resulting therefrom were obtained that show at 25° C. a viscosity lower by at least 20%, preferably at least 30%, and particularly preferably at least 40% compared to silylated polyurethanes that were produced with conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric or polymeric NCO-functionalized polyurethane prepolymers.
Advantageous silylated polyurethanes can further be obtained by a method according to the invention. A method according to the invention comprises the following steps:

- provision of NCO-functionalized polyol,
- reaction of the NCO-functionalized polyol of step I with organosilane, preferably with aminosilane.

An alternative embodiment of the method for the preparation of silylated polyurethanes according to the invention comprises the following steps:

- provision of a mixture of NCO-functionalized polyol and oligomeric and/or polymeric polyurethane prepolymers,
- reaction of the mixture of step I with organosilane, preferably with aminosilane.

In a preferred method according to the invention, NCO-functionalized polyol is used, which in turn is a method that comprises the following steps:

- I. provision of at least one isocyanate-containing compound (A),
- II. provision of at least one polyol (B),
- III. reaction of I with II in the presence of at least one catalyst, wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.

Further preferred embodiments for preparing the NCO-functionalized polyols usable in the method according to the invention are also to be taken from the above-mentioned preferred embodiments and also apply correspondingly to the methods for the preparation of silylated polyurethanes according to the invention.
In a preferred method according to the invention for the preparation of silylated polyurethanes, the NCO-functionalized polyol used therein from the production method of step III has a content of NCO-functionalized polyol on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %.
In a further preferred method according to the invention for the preparation of silylated polyurethanes, the NCO-functionalized polyol used therein from the production method of step III has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol. In this context, it is particularly preferable to sharply limit the processing or cleaning steps, in particular to carry out only one subsequent processing or cleaning step after step III. Most particularly preferably, one can dispense with any processing or cleaning steps after step III. Despite limiting or dispensing with the processing or cleaning steps, NCO-functionalized polyol can still be obtained having a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt % based on the weight of the NCO-functionalized polyol.
The NCO-functionalized polyols used in a particularly preferred method for the preparation of silylated polyurethanes shows a structure according to the structure perfection A_nB or general structure (1).
A further particularly preferred method for the preparation of silylated polyurethanes is characterized in particular in that the NCO-functionalized polyol used is composed of isocyanate-containing compound (A) as claimed in one of claims 10 to 13 and polyol (B) with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol.
In this case, it is particularly preferable for the isocyanate-containing compound (A) to be one of the isocyanate-containing compounds specifically refer tod herein. Most particularly preferable as isocyanate-containing compound (A) is isophorone diisocyanate (IPDI).
In the method according to the invention for the preparation of silylated polyurethanes, all of the catalysts mentioned herein can be used for the preparation of the NCO-functionalized polyol used in step III. Particularly preferred in this case are heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or dibutyltin dilaurate (DBTL) or a mixture thereof.
Furthermore, it is particularly preferable in the method according to the invention for the preparation of silylated polyurethanes to carry out the reaction of I with II for the preparation of the NCO-functionalized polyol used at temperatures depending on the catalyst and/or the catalyst amount according to the dependencies mentioned herein. In particular, reference is made to the embodiments mentioned herein with respect to the catalysts from group A and/or the catalysts from group B.
It is highly preferable in the method according to the invention for the preparation of silylated polyurethanes for the organosilane to be an aminosilane. Further most preferable are the aminosilanes mentioned herein as being particularly preferable.
Finally, it is particularly preferable to use a method according to the invention in preparing silylated polyurethanes.
Most particularly preferred is the use of one of the methods according to the invention mentioned herein, wherein the silylated polyurethanes obtained therefrom show viscosity at 25° C. that is at least 20%, preferably at least 30%, and particularly preferably at least 40% lower compared to silylated polyurethanes that were manufactured by methods in which conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric and/or polymeric NCO-functionalized polyurethane prepolymers, were used.

Further Embodiments

- 1. Polyurethane prepolymers obtainable due to a reaction of
  - I. at least one isocyanate-containing compound with a molecular weight of 120 Da to 1000 Da with
  - II. a hydroxyfunctionalized polymer with a number average molecular weight M_nof 3,500 to 100,000 Da, in the presence of a catalyst, characterized in that the course of molecular weight, measured by means of gas permeation chromatography, of the polyurethane prepolymers of 2,000 Da (x₁) to 200,000 Da (x₃) along the x axis has a first section with an area integral F_Iand a second section with an area integral Fu, the ratio of which F_II/F_Iis between 0 and 0.4 inclusively, wherein the first section extends from x₁to x₂and the second section extends from x₂to x₃, and x₂defines the extreme point between the last intensity maximum (M1a) in the first section, which is in the range of the molecular weight of the hydroxyfunctionalized polymer, and the following intensity maximum (M2) in the second section.
- 2. Polyurethane prepolymers according to embodiment 1, characterized in that the molar ratio of NCO groups to hydroxyl groups in the reaction of I with II is from 5.0:1 to 1.05:1, preferably from 4:1 to 1.5:1 and particularly preferably from 3.0:1 to 1.8:1.
- 3. Polyurethane prepolymers according to embodiment 1 or 2, characterized in that the peak (M1a) corresponds to the molecular weight region of a polyurethane prepolymer of formula (1) below,

- - Where n=x+y
    - n corresponds to number of OH groups in the polyal/functionality
- wherein R^isodenotes the structural unit of the isocyanate-containing compound and R^polydenotes the structural unit of the hydroxyfunctionalized polymer, wherein n is equal to x+y and n corresponds to the number of OH groups in the polyol (functionality).
- 4. Polyurethane prepolymers according to embodiment 1 to 3, characterized in that the isocyanate-containing compound is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′MDI) or 4,4′-diphenylmethane diisocyanate (4,4′-MDI), as well as mixtures thereof.
- 5. Polyurethane prepolymers according to one of embodiments 1 to 4, characterized in that the isocyanate-containing compound is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (MDI) or 4,4′-diphenylmethane diisocyanate (4,4′-MDI) as well as mixtures thereof and combinations with other isocyanate-containing compounds.
- 6. Polyurethane prepolymers according to one of embodiments 1 to 5, characterized in that the hydroxyfunctionalized polymer is selected from the group composed of polyether polyols, polyester polyols, polycarbonate polyols as well as mixtures of these polyols with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90000, particularly preferably 4,000 to 80,000 g/mol.
- 7. Polyurethane prepolymer according to one of embodiments 1 to 6, characterized in that the hydroxyfunctionalized polymer is selected from the group composed of polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene di- and -triols, polyols of higher functionality such as sorbitol, pentaerythritol-initiated polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryl-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO₂polyols, polytetrahydrofuran-based polyether (PTMEG), OH-terminated prepolymers based on the reaction of a polyether- or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols, polyester polyols, or mixtures thereof.
- 8. Polyurethane prepolymer according to one of embodiments 1 to 7, characterized in that the hydroxyfunctionalized polymer is selected from the group composed of polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol.
- 9. Polyurethane prepolymers according to one of embodiments 1 to 8, characterized in that the catalyst is selected from the group composed of metal-siloxane-silanol(ate) compounds, organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or zirconium and from the group of the tertiary amines or mixtures thereof.
- 10. Polyurethane prepolymers according to one of embodiments 1 to 9, characterized in that the temperature in the reaction of I with II is between 10° C. and 120° C., preferably between 15° C. to 100° C., particularly preferably between 20° C. and 90° C. and most particularly preferably between 25° C. and 85° C.
- 11. Polyurethane prepolymers according to one of embodiments 1 to 10, characterized in that the total catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the hydroxyfunctionalized polymer used.
- 12. Polyurethane prepolymers according to one of embodiments 1 to 11, characterized in that the catalyst is selected from the groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or a tertiary amine.
- 13. Polyurethane prepolymers according to embodiment 12, characterized in that in using a catalyst from group A, a reaction temperature of between 10° C. and 120° C., preferably between 15° C. to 100° C., particularly preferably between 20° C. and 90° C. and most particularly preferably between 25° C. and 85° C. is used.
- 14. Polyurethane prepolymers according to one of embodiments 12 to 13, characterized in that in using a catalyst from group A, the amount of catalyst A is selected between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm.
- 15. Polyurethane prepolymers according to embodiment 12, characterized in that in using a catalyst from group B, a reaction temperature of 20° C. to 80° C., preferably from 20° C. to 70° C., particularly preferably from 25° C. to 50° C. is used.
- 16. Polyurethane prepolymers according to embodiment 12 or 15, characterized in that in using a catalyst from group B, the amount of catalyst B is selected between 1 ppm to 1000 ppm, preferably between 2 ppm to 250 ppm, particularly preferably between 3 ppm to 100 ppm.
- 17. Polyurethane prepolymers according to one of embodiments 12 to 14, characterized in that catalyst A is a metal-siloxane-silanol(ate) compound and has general structure (II),

- wherein
  - X¹, X²and X³are selected independently of one another from Si or M¹, wherein M¹is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from the group composed of L², R⁵, R⁶and R⁷, wherein L²is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from the group composed of —OH, —O-methyl, —O— ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl; R¹, R², R³, R⁴, R⁵, R⁶and R⁷are selected independently of one another from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C₃to C₈cycloalkyl, optionally substituted C₂to C₂₀alkenyl and optionally substituted C₅to C₁₀aryl; Y¹and Y²denote independently of each another —O-M²-L³ _Δ, or Y¹and Y²are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from the group composed of —OH and —O—(C1 to C10 alkyl). in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from the group composed of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M²is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and
  - X⁴denotes -M³L¹ _Δ or M³and Q¹and Q²denote in each case denote H or a single bond linked to M³, wherein L¹is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O— octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
  - or
  - X⁴denotes -M³L¹ _Δ and Q²H denotes a single bond linked to M³and Q¹denotes H, M⁴L⁴ _Δ or —SiR⁸, wherein M⁴is selected from the group composed of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group composed of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L⁴is selected from the group composed of —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from the group composed of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein R⁸is selected from the group composed of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl,
  - or
  - X⁴, Q¹and Q²denote independently of one another -M³L¹ _Δ,
  - or
  - X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes -M⁴L⁴ _Δ,
  - or
  - X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and
  - Q¹denotes a single bond linked to the M³atom of X⁴.
- 18. Polyurethane prepolymer according to embodiment 12 or 15, characterized in that catalyst B is selected from the group composed of tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂, where R denotes e.g. iso-propyl, n-butyl, iso-butyl), such as isopropyl-n-butyl titanate; titanium-acetylacetonate chelates such as di-isopropoxy-bis(acetylacetonate) titanate, di-isopropoxy-bis(ethyl acetoacetate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethyl acetoacetate) titanate, tri-isopropoxide-bis(acetylacetonate) titanate, zirconium tetraalkylates such as zirconium tetraethylate, zirconium tetrabutylate, zirconium tetrabutyrate, zirconium tetrapropylate, zirconium carboxylates such as zirconium diacetate; zirconium acetylacetonate chelates such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium(bisacetylacetonate), aluminum trisalkylates such as aluminum triisopropylate, aluminum trisbutylate; aluminum-acetylacetonate chelates such as aluminum tris(acetylacetonate) and aluminum tris(ethyl acetoacetate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II)-2-ethyl hexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethylmercaptides, dibutylmercaptides, dioctylmercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II)-2-ethyl hexanoate or zinc(II)-neodecanoate, mixtures of bismuth and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids such as bismuth(III)-tris(2-ethylhexanoate) and bismuth(III)-tris(neodecanoate) as well as bismuth complex compounds, organolead compounds such as lead octylate, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undec-7-ene (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof.
- 19. Polyurethane prepolymer according to embodiment 18, characterized in that catalyst B is selected from the group composed of dibutyltin dilaurate (DBTL), tin(II)-2-ethyl hexanoate (tin octoate), zinc(II)-2-ethyl hexanoate, zinc(II)-neodecanoate, bismuth(III)-tris(2-ethylhexanoate), bismuth(III)-tris(neodecanoate) or mixtures thereof.
- 20. Polyurethane prepolymer according to one of embodiments 12 to 19, characterized in that the at least one catalyst A and/or at least one catalyst B is selected from the group of the tin- or titanium organic compounds.
- 21. Polyurethane prepolymer according to one of embodiments 12 to 20, characterized in that catalyst A is selected from the group of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).
- 22. Polyurethane prepolymers according to embodiment 21, characterized in that catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).
- 23. Polyurethane prepolymer according to embodiment 19 or 20, characterized in that catalyst B is dibutyltin dilaurate (DBTL).
- 24. Silylated polyurethanes obtainable by reaction of polyurethane prepolymers according to one of embodiments 1 to 23 with an organosilane.
- 25. Silylated polyurethanes according to embodiment 24, characterized in that the silylated polyurethane has at least two terminal groups of general formula (V),

- wherein
  - X is C, Si or a heteroatom, optionally having, depending on its covalency, one or more radicals R¹, preferably C, N, O, P, S, particularly preferably C, N or O, most particularly preferably N or O is and which in each case is bonded to a carbon in the polymer backbone,
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - each Y independently denotes either O or a direct bond of the Si atom to the respective radical R⁹, R¹⁰or R¹¹, preferably at least one Y denotes O,
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C16 alkyl group, an optionally substituted, linear, or branched C2 to C16 alkenyl group or an optionally substituted, linear, or branched C2 to C16-alkinyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group or a radical of general structure (Vb),
  - R¹²and R¹⁴in each case denote independently of each other H or a radical from the group composed of —R¹⁵, —COOR¹⁵and —CN,
  - R¹³denotes H or a radical from the group composed of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵and —SO₂OR¹⁵,
  - R¹⁵denotes a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom,
  - R⁹, R¹⁰and R¹¹denote independently of one another H, an optionally substituted, linear, or branched C1 to C5 alkyl group, an optionally substituted, linear, or branched C2 to C10 alkenyl group or an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group,
  - m is 0 or 1, and when m=0, the Si atom is directly bonded to a carbon in the polymer backbone.
- 26. Silylated polyurethanes according to embodiment 25, characterized in that the organosilane is selected from general structure (VIII) or is a mixture thereof,

- wherein
  - R⁷is H,
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C25 alkyl group, an optionally substituted, linear, or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of general structure (Vb),
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, and when R*=0, the Si atom is directly bonded to the N atom,
  - R¹²and R¹⁴in each case denote independently of each other H or a radical from the group composed of —R⁵, —COOR¹⁵and —CN,
  - R¹³denotes H or a radical from the group composed of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵and —SO₂OR¹⁵,
  - R¹⁵denotes a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom,
  - R⁹, R¹⁰, R¹¹and R* are as defined according to claim 25 and
  - each Y independently denotes either O or a direct bond of the Si atom to the respective radical R⁹, R¹⁰or R¹¹, preferably at least one Y denotes O.
- 27. Silylated polyurethanes according to embodiment 26, characterized in that at least one organosilane is selected from general structure (VIII) or is a mixture thereof,

- wherein
  - R⁸denotes H, an optionally substituted, linear, or branched C1 to C10 alkyl group, an optionally substituted, linear, or branched C2 to C10 alkenyl group or an optionally substituted, linear, or branched C2 to C10 alkinyl group, an optionally substituted C4 to C10 cycloalkyl group or an optionally substituted C4 to C10 aryl group or a succinic acid derivative according to general structure (Vb) according to claim 26,
  - R* denotes 0 or an optionally substituted, linear, or branched C1 to C20 alkyl group or an optionally substituted C4 to C12 cycloalkyl group or an optionally substituted C4 to C12 aryl group, preferably an optionally substituted, linear, or branched C1 to C15 alkyl group, particularly preferably a C1 alkyl group (=alpha-silane) or is a C3 alkyl group (=gamma-silane), and when R*=0, the Si atom is directly bonded to the N atom,
  - R⁹, R¹⁰, R¹¹are as defined according to claim 25, preferably R⁹, R¹⁰, R¹¹is/are a methyl or ethyl group or mixtures thereof and
  - the Y in Y—R⁹and Y—R¹⁰denotes O and the Y in Y—R¹¹denotes either O or a direct bond of the Si atom to the respective radical R¹¹.
- 28. Silylated polyurethanes according to embodiment 24, characterized in that the organosilane corresponds to an organosilane of formula (IX),

- - wherein the two radicals R¹⁶and R¹⁷in each case are independent of each other and the radical R¹⁶is a linear or branched, monovalent hydrocarbon radical with 1 to 8 C atoms, in particular a methyl or ethyl group, the radical R¹⁷is an acyl radical or is a linear or branched, monovalent hydrocarbon radical with 1 to 5 C atoms, in particular a methyl or ethyl group, preferably a methyl group, the Index a is 0 or 1 or 2, in particular 0, and the radical R¹⁶is a linear or branched, divalent hydrocarbon radical with 1 to 12 C atoms, which optionally has cyclic fractions and optionally one or more heteroatoms, in particular one or more nitrogen atoms, in particular an alkylene group with 1 to 6 C atoms, preferably 2 to 6 C atoms, in particular a propylene group, and R¹⁹is a hydrogen atom or a cyclic, linear or branched, monovalent hydrocarbon radical with 1 to 20 C atoms, which optionally has cyclic fractions, or a radical of the following formula:

- - wherein the radicals R²⁰and R²¹in each case denote independently of each other a hydrogen atom or a radical from the group composed of —R²³, —COOR²³and —CN, the radical R²²is a hydrogen atom or a radical from the group composed of —CH₂—COOR*, —COOR²³, —CONHR²³, —CON(R²³)₂, —CN, —NO₂, —PO(OR²³)₂, —SO₂R²³and —SO₂OR²³, and the radical R²³is a hydrocarbon radical with 1 to 20 C atoms optionally having at least one heteroatom, as well as mixtures thereof.
- 29. Silylated polyurethanes according to one of embodiments 24 to 28, characterized in that the aminosilane is selected from the group of the primary aminosilanes, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane, the secondary aminosilanes, preferably N-butyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, the group of products obtainable from the Michael like addition of primary aminosilanes such as 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid- and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably N-(3-trimethoxysilyl-propyl)-amino-succinic acid dimethyl- and -diethylester.
- 30. Silylated polyurethanes according to one of embodiments 24 to 29, characterized in that the aminosilane is an N-alkylamino silane, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane.
- 31. Composition containing silylated polyurethanes according to embodiment 24 to 30.
- 32. Composition containing one or more polyurethane prepolymers according to one of embodiments 1 to 23.
- 33. Use of the polyurethane prepolymers according to one of embodiments 1 to 23 for the preparation of polyurethan elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems, which are used as polyurethane foams, construction materials, paints, coatings, adhesives and sealants, casting compounds, films or PUR elastomers.
- 34. Use of the polyurethane prepolymers according to one of embodiments 1 to 23 for the preparation of reactive PU compositions, preferably in aqueous 1K- or 2K-PU compositions.

EXAMPLES

1. GPC Data

Device and Parameters for STD-GPC Measurement:

Chromatography System:

- Degasser: Agilent 1260 Infinity Degasser
- Pump: Agilent 1260 Infinity isoPump
- Autosampler: Agilent 1260 Infinity ALS
- Column oven: Agilent 1290 Infinity II TCC
- RI detector: Agilent 1260 Infinity RID
- Software: PSS WinGPC UniChrom V 8.31, Build 8417

Chromatographic Conditions:

- DIN: DIN EN ISO 16014-1, DIN 55672-1
- Column: 1. PLgel 5 p Mixed D (Agilent Technologies)
- 2. PLgel 5μ Mixed D (Agilent Technologies)
- 3. PLgel 3 μm Mixed E (Agilent Technologies)
- Mobile phase: tetrahydrofuran
- Flow rate: 1 mL/min
- Temperature: 35° C.
- Injection volume: 100 μL
- Sample concentration: 1 g/L
- Molecular weight standards:
- PSS Polymer Standards Service GmbH, Mainz; Germany
- M_p[Da]: 66,000; 42,400; 25,500; 15,700; 8,680; 6,540; 4,920; 3,470; 2,280; 1,306; 370; 266
  - The calibration curve is valid between 266 Da and 66,000 Da. Values outside of these limits are extrapolated.

II. Viscosity

The viscosities were determined using a Brookfield Rheometer DV-3 T Extra at 25° C. The spindle size and rotational speed of the spindle were selected such that torque >90%.

III Infrared (IR) Spectroscopy:

IR monitoring was carried out with a ThermoScientific Nicolet iS5 and iD7ATR unit. Evaluation was carried out with Omnic software.

Examples I)

Chemicals Used:

- Acclaim 18200 (Covestro AG; low monol polyoxypropylene diol, OH number 6.0 mg KOH/g, water content approx. 0.02% by weight)
- 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate (Desmodur® I, Covestro AG, Leverkusen)
- TiPOSS (heptaisobutyl POSS-titanium(IV) ethoxide), 20% dissolved in Hexamoll® DINCH, BASF)
- DBTL (dibutyltin dilaurate) BNT chemicals
- DBA (di-n-butylamine) purity >99%, TCI Chemicals
- N-[3-(trimethoxysilyl)propyl]butylamine, DOG Deutsche Olfabrik
- VTMO, vinyltrimethoxysilane, Acros Organics

A) Production of Selective Polyurethane Prepolymers

Example 1

200 g (11 mmol) of polypropylene glycol with an approximate number average molecular weight M_nof 18,000 g/mol (OH number=6.0±1.0 mg KOH/g) was placed in a 500 mL three-necked flask and dried under a vacuum at 80° C. for 1 h. The vacuum was then broken with nitrogen. The polyol was cooled to 25° C. 0.01 g (0.016 mmol) of DBTL catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added while stirring. As soon as the theoretical NCO content of 0.52 wt % was reached, the viscosity of the NCO prepolymer was determined [46000 mPas (25° C., Brookfield viscosimeter)]. For GPC analysis, the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred for 20 min at 25° C. The reaction was followed by IR spectroscopy (disappearance of the NCO band (2270 cm⁻¹). The ratio of the area integral F_Iin the first section (x₁to x₂) of the molecular weight distribution to the area integral F_IIin the second section of the molecular weight distribution F_II/F_Iis 0.29.

Example 2

200 g (11 mmol) of polypropylene glycol with an approximate number average molecular weight M_nof 18,000 g/mol (OH number=6.0±1.0 mg KOH/g) was placed in a 500 mL three-necked flask and dried under a vacuum at 80° C. for 1 h. The vacuum was then broken with nitrogen. The polyol was cooled to 25° C. 0.01 g (0.011 mmol, pure substance) of TiPOSS-catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added and the reaction mixture was stirred. As soon as the theoretical NCO content of 0.52 wt % was reached, the viscosity of the NCO prepolymer was determined [44,000 mPas (25° C., Brookfield viscosimeter)]. For GPC analysis, the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred for 20 min at 25° C. The reaction was followed by IR spectroscopy (disappearance of the NCO band (2270 cm⁻¹). The ratio of the area integral F_Iin the first section (x₁to x₂) of the molecular weight distribution to the area integral F_IIin the second section (x₂to x₃) of the molecular weight distribution F_II/F_Iis 0.27.
Examples 3 to 6 were prepared according to the procedure of examples 1 and 2.

	TABLE 1

	Not
	according

Example		Catalyst	Reaction	Viscosity	to the	Area
no.	Catalyst	amount	temperature	[mPas]	invention x	ratio

1	DBTL	50	ppm	25° C.	46,000		0.29
2	TiPOSS	50	ppm	25° C.	44,000		0.27
3	TiPOSS	10	ppm	80° C.	43,000
4	TiPOSS	50	ppm	80° C.	48,000		0.23
5	TiPOSS	37.5	ppm	40° C.	48,000
6	TiPOSS	84	ppm	25° C.	43,000
7	DBTL	50	ppm	80° C.	120,800	x	0.43

B) Production of the Silane-Terminated Polymers (STP), Also Silylated Polymers Referred to as Silane-Terminated Polyols, from the Reaction of Isocyanate Prepolymer

Example 8

150.2 g (8.3 mmol) of polypropylene glycol with an approximate number average molecular weight M_nof 18,000 g/mol (OH number=6.0±1.0 mg KOH/g) was placed in a 500 mL three-necked flask and dried under a vacuum at 90° C. for 1 h. The vacuum was then broken with nitrogen. The polyol was cooled to 80° C. 1.5 mg (0.0015 mmol, pure substance) TiPOSS catalyst and 4.01 g (18 mmol) of isophorone diisocyanate (IPDI) were added while stirring. As soon as the theoretical NCO content of 0.52 wt % was reached, 4.97 g (21 mmol) of N-[3-(trimethoxysilyl)propyl]butylamine] was added while stirring and simultaneously cooled to 25° C. The reaction was followed by IR spectroscopy (disappearance of the NCO band (2270 cm¹). 2 wt % of VTMO was added to the finished STP. The viscosity of the product was 43,000 mPas (25° C., Brookfield viscosity).
In Table 1a, examples are given of NCO-functionalized polyols produced according to the invention or oligomeric polyurethane prepolymers not according to the invention (wherein at least two or mehr polyol molecules are linked to the diisocyanates via polyurethane bonds)—Examples 1 to 10 show the viscosities of the NCO functional compounds. Examples 11 to 19 show the viscosities of the silylated polyurethanes produced from the NCO functional compounds (produced by reaction of the respective NCO functional compounds with aminosilane).

	TABLE 1a

	Not
	according

Example	MW of		Catalyst	Reaction	Viscosity	to the	Area
no.	polyol	Catalyst	amount	temperature	[mPas]	invention x	ratio

1	18,000	DBTL	50	ppm	25°	C.	46,000*		0.29
2	18,000	TiPOSS	50	ppm	25°	C.	44,000*		0.27
3	18,000	TiPOSS	5	ppm	120°	C.	180,000*	x
4	18,000	TiPOSS	2.5	ppm	120°	C.	88,000*	x
5	18,000	TiPOSS	50	ppm	80°	C.	48,000*		0.23
6	18,000	TiPOSS	10	ppm	80°	C.	42,000*
7	18,000	TiPOSS	37.5	ppm	40°	C.	48,000*
8	18,000	TiPOSS	5000	ppm	25°	C.	>120,000*	x
9	18,000	TiPOSS	84	ppm	25°	C.	43,000*
10	18,000	DBTL	50	ppm	80°	C.	120,800*	x	0.43
11	12,000	TiPOSS	50	ppm	43°	C.	21,900**
12	12,000	TiPOSS	50	ppm	31°	C.	20,870**
13	12,000	TiPOSS	16	ppm	60°	C.	19,840**
14	12,000	DBTL	1200	ppm	43°	C.	43,000**	x
15	8,000	TiPOSS	50	ppm	25°	C.	11,300**
16	8,000	DBTL	50	ppm	60°	C.	50,000**	x
17	8,000	DBTL	50	ppm	43°	C.	16,752**
18	4,000	TiPOSS	1300	ppm	50°	C.	61,000**	x
19	4,000	TiPOSS	135	ppm	20°	C.	6,363**

*NCO-functionalized polyol or if x, then not according to the invention, as oligomeric polyurethane prepolymer (=at least two polyol units per molecule of the NCO-functionalized compound).
** Silylated polyurethan produced from a reaction of the respective NCO-functionalized polyols or the oligomeric polyurethane prepolymers not according to the invention with aminosilane

Claims

1. Silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with organosilane.

2. Silylated polyurethanes as claimed in claim 1, characterized in that the NCO-functionalized polyol corresponds to the NCO-functionalized polyol has an (I),

wherein

R^isodenotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R^polydenotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B) (=functionality).

3. Silylated polyurethanes as claimed in claim 1, characterized in that the NCO-functionalized polyol as an A_nB-structure, wherein A denotes the isocyanate-containing compound(s) used for preparing the NCO-functionalized polyol and B denotes the polyol used and n corresponds to the number of free OH groups in the polyol used (B).

4. Silylated polyurethanes as claimed in claim 1, characterized in that the NCO-functionalized polyol is obtainable due to a reaction of

I. at least one isocyanate-containing compound (A) with

II. at least one polyol (B), in the presence of at least one catalyst, and wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.

5. Silylated polyurethanes as claimed in claim 4, characterized in that an asymmetrical isocyanate-containing compound (A) with a molecular weight of 120 g/mol to 1000 g/mol is used.

6. Silylated polyurethanes as claimed in claim 4, characterized in that a polyol (B) with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably from 4,000 to 80,000 g/mol is used.

7. Silylated polyurethanes as claimed in claim 4, characterized in that the reaction of I with II is carried out at temperatures of 15 to 70° C., preferably from 25 to 65° C.

8. Silylated polyurethanes as claimed in claim 4, characterized in that the NCO-functionalized polyol obtainable from the reaction has, after the reaction is carried out, a content of NCO-functionalized polyol according to structure (I) on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %, wherein the structure (I) is:

wherein

9. Silylated polyurethanes as claimed in claim 1, characterized in that the NCO-functionalized polyol has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol.

10. Silylated polyurethanes as claimed claim 4, characterized in that the isocyanate-containing compound (A) has at least two NCO groups.

11. Silylated polyurethanes as claimed in claim 4, characterized in that the isocyanate-containing compound (A) is a diisocyanate.

12. Silylated polyurethanes as claimed in claim 4, characterized in that the isocyanate-containing compound (A) is asymmetrical.

13. Silylated polyurethanes as claimed in claim 12, characterized in that the asymmetrical isocyanate-containing compound (A) is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof.

14. Silylated polyurethanes as claimed in claim 4, characterized in that the polyol (B) is a hydroxyfunctionalized compound, which is preferably selected from the group of the polyether polyols, polyester polyols, polycarbonate polyols as well as mixtures of these polyols.

15. Silylated polyurethanes as claimed in claim 4, characterized in that the polyol (B) is selected from polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene di- and -triols, polyols of higher functionality such as sorbitol, pentaerythritol-initiated polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryl-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO₂polyols, polytetrahydrofuran-based polyether (PTMEG), OH-terminated prepolymers based on the reaction of a polyether- or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols, polyester polyols, or mixtures thereof.

16. Silylated polyurethanes as claimed in claim 1, characterized in that the polyol is selected from polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol.

17. Silylated polyurethanes as claimed in claim 4, characterized in that the catalyst is selected from metal-siloxane-silanol(ate) compounds, organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or zirconium and from the group of the tertiary amines or mixtures thereof.

18. Silylated polyurethanes as claimed in claim 4, characterized in that the catalyst is selected from groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or a tertiary amine.

19. Silylated polyurethanes as claimed in claim 4, characterized in that a catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the polyol (B) used.

20. Silylated polyurethanes as claimed in claim 18, characterized in that in using a catalyst from group A, a reaction temperature of between 15° C. and 70° C., preferably between 25° C. to 65° C., particularly preferably between 30° C. and 50° C. and most particularly preferably between 30° C. and 45° C. is used.

21. Silylated polyurethanes as claimed in claim 18, characterized in that in using a catalyst from group A, the amount of catalyst A is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm, based on the total weight of the polyol (B) used.

22. Silylated polyurethanes as claimed in claim 18, characterized in that in using a catalyst from group B, a reaction temperature of 20° C. to 70° C., preferably from 25° C. to 50° C., particularly preferably from 30° C. to 45° C., is used.

23. Silylated polyurethanes as claimed in claim 18, characterized in that in using a catalyst from group B, the amount of catalyst B is between 1 ppm to 1000 ppm, preferably between 2 ppm to 250 ppm, particularly preferably between 3 ppm to 100 ppm, based on the total weight of the polyol (B) used.

24. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst A is a metal-siloxane-silanol(ate) compound and has general structure (II),

wherein

X¹, X²and X³are selected independently of one another from Si or M¹, wherein M¹is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z²and Z³are selected independently of one another from L², R⁵, R⁶and R⁷, wherein L²is selected from —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L²is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl; R¹, R², R³, R⁴, R⁵, R⁶and R⁷are selected independently of one another from optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl; Y¹and Y²denote independently of each another —O-M²-L³ _Δ, or Y¹and Y²are taken together and together denote —O-M²(L³ _Δ)-O— or —O—, wherein L³is selected from —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L³is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M²is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

and

X⁴denotes -M³L¹ _Δ or M³and Q¹and Q²denote in each case denote H or a single bond linked to M³, wherein L¹is selected from —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L¹is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M³is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

or

X⁴denotes -M³L¹ _Δ and Q²H denotes a single bond linked to M³and Q1 denotes H, M⁴L⁴ _Δor —SiR⁸, wherein M⁴is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L⁴is selected from OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L⁴is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein R⁸is selected from optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl,

or

X⁴, Q¹and Q²denote independently of one another -M³L¹ _Δ,

or

X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes -M⁴L⁴ _Δ,

or

X⁴denotes —Si(R⁸)—O-M³L¹ _Δ, Q²denotes a single bond linked to the Si atom of X⁴and Q¹denotes a single bond linked to the M³atom of X⁴.

25. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst A is the metal-siloxane-silanol(ate) compound of structure (IV),

wherein

X⁴is selected from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most particularly preferably from Ti and Sn, most particularly preferably Ti, and X⁴is linked with OR, wherein R is selected from —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, Z¹, Z²and Z³in each case denote independently of one another C1 to C20 alkyl, C3 to C8 cycloalkyl, C2 to C20 alkenyl and C5 to C10 aryl, and in particular are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl- and phenyl, and benzyl, and R¹, R², R³and R⁴in each case denote independently of one another C1 to C20 alkyl, C3 to C8 cycloalkyl, C2 to C20 alkenyl, and C5 to C10 aryl, and in particular are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl.

26. Silylated polyurethanes as claimed in claim 25, characterized in that X⁴is Sn or Ti, and X⁴is linked with OR, wherein R is selected from —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, preferably -ethyl, -propyl or -butyl, particularly preferably -ethyl or -butyl, and Z¹, Z²and Z³as well as R¹, R², R³and R⁴are selected independently of one another from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl- and phenyl, and benzyl, and preferably independently of one another are isopropyl- or isobutyl, particularly preferably Z¹, Z²and Z³as well as R¹, R², R³and R⁴isobutyl-.

27. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or mixtures thereof.

28. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).

29. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst B is selected from tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂, where R denotes e.g. iso-propyl, n-butyl, iso-butyl), such as isopropyl-n-butyl titanate; titanium-acetylacetonate chelates such as di-isopropoxy-bis(acetylacetonate) titanate, di-isopropoxy-bis(ethyl acetoacetate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethyl acetoacetate) titanate, tri-isopropoxide-bis(acetylacetonate) titanate, zirconium tetraalkylates such as zirconium tetraethylate, zirconium tetrabutylate, zirconium tetrabutyrate, zirconium tetrapropylate, zirconium carboxylates such as zirconium diacetate; zirconium acetylacetonate chelates such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium(bisacetylacetonate), aluminum trisalkylates such as aluminum triisopropylate, aluminum trisbutylate; aluminum-acetylacetonate chelates such as aluminum tris(acetylacetonate) and aluminum tris(ethyl acetoacetate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II)-2-ethyl hexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethylmercaptides, dibutylmercaptides, dioctylmercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II)-2-ethyl hexanoate or zinc(II)-neodecanoate, mixtures of bismuth and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids such as bismuth(III)-tris(2-ethylhexanoate) and bismuth(III)-tris(neodecanoate) as well as bismuth complex compounds, organolead compounds such as lead octylate, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undec-7-ene (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof.

30. Silylated polyurethanes as claimed in claim 18, characterized in that catalyst B is dibutyltin dilaurate (DBTL) ist.

31. Silylated polyurethanes as claimed in claim 1, characterized in that the organosilane is an aminosilane.

32. Silylated polyurethanes as claimed in claim 31, characterized in that the aminosilane is selected from the group of the primary aminosilanes, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane, the secondary aminosilanes, preferably N-butyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, from the group of products obtainable from the Michael like addition of primary aminosilanes such as 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably N-(3-trimethoxysilyl-propyl)-amino-succinic acid dimethyl- and -diethylesters.

33. Silylated polyurethanes as claimed in f claim 1, characterized in that the aminosilane is an N-alkylamino silane, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane.

34. Silylated polyurethanes, characterized by being obtainable due to a reaction of NCO-functionalized polyol with organosilane, preferably with aminosilane, particularly preferably with an aminosilane as claimed in claim 33, wherein the polyol used in preparing the NCO-functionalized polyol used in the reaction is a polyol (B) with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol and the isocyanate-containing compound (A) used is asymmetrical, preferably an asymmetrical isocyanate-containing compound (A) which is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof.

35. Silylated polyurethanes as claimed in claim 1, characterized in that the silylated polyurethanes are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have a Shore A hardness in a cured state according to ASTM D2240-15 in the range of 0 to 100, preferably in the range of 15 to 100, more preferably in the range of 20 to 95, particularly preferably in the range of 25 to 90.

36. Silylated polyurethanes as claimed in f claim 1, characterized in that the silylated polyurethanes are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have an elongation at break in a cured state according to DIN 53504-S2 (:2017-03) in the range of 0 to 1000%, preferably in the range of 15 to 500%, particularly preferably in the range of 50 to 250%.

37. Composition containing silylated polyurethanes as claimed in claim 1.

38. Formulation containing silylated polyurethanes as claimed in claim 1.

39. Use of silylated polyurethanes as claimed in claim 1 in CASE applications (coatings, adhesives, sealants and elastomers) and/or elastomeric materials.

40. Composition containing one or more NCO-functionalized polyols as claimed in claim 2.

41. Method of using NCO-functionalized polyols comprising preparing silylated polyurethane as claimed in claim 2 with said NCO-functionalized polyols.

42. Method of using NCO-functionalized polyols as claimed in claim 41, characterized in that the silylated polyurethanes resulting therefrom show viscosity at 25° C. that is at least 20%, preferably at least 30%, and particularly preferably at least 40% lower compared to silylated polyurethanes that were produced with conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric and/or polymeric NCO-functionalized polyurethane prepolymers.

43. Method for the preparation of silylated polyurethanes comprising the following steps:

provision of NCO-functionalized polyol,

reaction of NCO-functionalized polyol with organosilane, preferably with aminosilane.

44. Method for the preparation of silylated polyurethanes comprising the following steps:

provision of a mixture of NCO-functionalized polyol and oligomeric and/or polymeric polyurethane prepolymers,

reaction of the provided mixture with organosilane, preferably with aminosilane.

45. Method as claimed in claim 43, wherein the NCO-functionalized polyol in a method that comprises the following steps:

I. provision of at least one isocyanate-containing compound (A),

II. provision of at least one polyol (B),

III. reaction of I with II in the presence of at least one catalyst, wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.

46. Method as claimed in claim 45, characterized in that the reaction of I with II is carried out at temperatures of 15 to 70° C., preferably 25 to 65° C.

47. Method as claimed in claim 45, characterized in that the NCO-functionalized polyol of step III has a content of NCO-functionalized polyol on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %.

48. Method as claimed in claim 45, characterized in that the NCO-functionalized polyol of step III has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol.

49. Method as claimed in claim 43, characterized in that the NCO-functionalized polyol has a structure (I):

wherein

50. Method as claimed in claim 43, characterized in that the NCO-functionalized polyol is composed of isocyanate-containing compound (A), wherein the isocyanate-containing compound (A) has at least two NCO groups, and polyol (B) is composed with a number average molecular weight M_nof 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol.

51. Method as claimed in claim 45, characterized in that the isocyanate-containing compound (A) is an asymmetrical isocyanate-containing compound (A) which is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof.

52. Method as claimed in claim 51, characterized in that the isocyanate-containing compound (A) is isophorone diisocyanate (IPDI).

53. Method as claimed in claim 45, characterized in that in step III, one or more catalyst(s) is/are selected from metal-siloxane-silanol(ate) compounds, organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or zirconium and from the group of the tertiary amines or mixtures thereof.

54. Method as claimed in claim 45, characterized in that the catalyst is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or dibutyltin dilaurate (DBTL) or a mixture thereof.

55. Method as claimed in claim 45, characterized in that the reaction of I with II is carried out at temperatures depending on the catalyst and/or a catalyst amount, wherein the catalyst is selected from groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or a tertiary amine, and wherein the catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the polyol (B) used.

56. Method as claimed in claim 43, characterized in that the organosilane is an aminosilane and is selected from an N-alkylamino silane, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane.

57. Use of a method in preparing silylated polyurethanes as claimed in claim 43.

58. Use of the method as claimed in claim 57, characterized in that the silylated polyurethanes show viscosity at 25° C. that is at least 20%, preferably at least 30%, and particularly preferably at least 40% lower compared to silylated polyurethanes that were manufactured by methods in which conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric and/or polymeric NCO-functionalized polyurethane prepolymers, were used.

59. Silylated polyurethanes produced according to one of the above methods as claimed in claim 43.